WorldWideScience

Sample records for conjugated polymers polythiophenes

  1. Polythiophenes Comprising Conjugated Pendants for Polymer Solar Cells: A Review

    Directory of Open Access Journals (Sweden)

    Hsing-Ju Wang

    2014-03-01

    Full Text Available Polythiophene (PT is one of the widely used donor materials for solution-processable polymer solar cells (PSCs. Much progress in PT-based PSCs can be attributed to the design of novel PTs exhibiting intense and broad visible absorption with high charge carrier mobility to increase short-circuit current density (Jsc, along with low-lying highest occupied molecular orbital (HOMO levels to achieve large open circuit voltage (Voc values. A promising strategy to tailor the photophysical properties and energy levels via covalently attaching electron donor and acceptor pendants on PTs backbone has attracted much attention recently. The geometry, electron-donating capacity, and composition of conjugated pendants are supposed to be the crucial factors in adjusting the conformation, energy levels, and photovoltaic performance of PTs. This review will go over the most recent approaches that enable researchers to obtain in-depth information in the development of PTs comprising conjugated pendants for PSCs.

  2. Electrochromic in conjugated polymers

    International Nuclear Information System (INIS)

    Picado Valenzuela, Alfredo

    2007-01-01

    This revision considered object the description of one of the materials with the greatest potential in the field of electrochromic (mainly in the visible region): the conjugated polymers (CP), area of enormous potential both now and in a short time ahead. The CP are insulating materials and organic semiconductors in a state not doped. They can be doped positively or negatively being observed a significant increase in the conductivity and being generated a color change in these materials. The understanding of how optical properties vary based on the chemical structure of the polymer or its mixtures and more precisely of the alternatives that can be entered into the conjugated system or π system to obtain a material that besides to be flexible, environmentally stable, presents the colored states. The revision was centred chiefly in the polypyrrole (Ppy), the polythiophene (PTh) and their derivatives such as poly (3.4-ethylenedioxythiophene) (PEDOT). The advantage of using monomers with variable structure, to adjust the composition of the copolymer, or to blend with the PC, allows to obtain a variety of colored states that can be modulated through the visible spectrum and even with applications to wavelengths outside of this region. Because the PC presented at least two different colored states can be varied continuously as a function of the voltage applied. In some cases, they may submit multicoloured statements, which offers a range of possibilities for their application in flexible electronic devices type screens and windows. Applications include smart windows, camouflage clothing and data screens. This type of material is emerging as one of the substitutes of the traditional inorganic semiconductor, with the advantage of its low cost, high flexibility and the possibility to generate multiple colors through the handling of the monomers in the structure and control of energy of his band gap. (author) [es

  3. Electrical conductivity study on polythiophenes films

    International Nuclear Information System (INIS)

    Youm, I.; Cadene, M.

    1994-10-01

    The electrical conduction mechanism of two classes of polythiophenes: polythiophene (PT) and poly(3-methylthiophene) (PMT) films containing various levels of doping counter-ions was investigated. The temperature dependence of electrical conductivity obeys the Mott equation based on variable range hopping. The dimension of the variable range hopping is correlated with the structure of the conducting polymer. It seems for these polymers that carrier transport via mobile conjugational defects does not play a detectable role. (author). 17 refs, 3 figs, 1 tab

  4. Conjugated Polymer Solar Cells

    National Research Council Canada - National Science Library

    Paraschuk, Dmitry Y

    2006-01-01

    This report results from a contract tasking Moscow State University as follows: Conjugated polymers are promising materials for many photonics applications, in particular, for photovoltaic and solar cell devices...

  5. Polymers for Protein Conjugation

    Directory of Open Access Journals (Sweden)

    Gianfranco Pasut

    2014-01-01

    Full Text Available Polyethylene glycol (PEG at the moment is considered the leading polymer for protein conjugation in view of its unique properties, as well as to its low toxicity in humans, qualities which have been confirmed by its extensive use in clinical practice. Other polymers that are safe, biodegradable and custom-designed have, nevertheless, also been investigated as potential candidates for protein conjugation. This review will focus on natural polymers and synthetic linear polymers that have been used for protein delivery and the results associated with their use. Genetic fusion approaches for the preparation of protein-polypeptide conjugates will be also reviewed and compared with the best known chemical conjugation ones.

  6. Photoluminescence in conjugated polymers

    International Nuclear Information System (INIS)

    Furst, J.E.; Laugesen, R.; Dastoor, P.; McNeill, C.

    2002-01-01

    Full text: Conjugated polymers combine the electronic and optical properties of semiconductors with the processability of polymers. They contain a sequence of alternate single and double carbon bonds so that the overlap of unhybridised p z orbitals creates a delocalised ρ system which gives semiconducting properties with p-bonding (valence) and p* -antibonding (conduction) bands. Photoluminesence (PL) in conjugated polymers results from the radiative decay of singlet excitons confined to a single chain. The present work is the first in a series of studies in our laboratory that will characterize the optical properties of conjugated polymers. The experiment involves the illumination of thin films of conjugated polymer with UV light (I=360 nm) and observing the subsequent fluorescence using a custom-built, fluorescence spectrometer. Photoluminesence spectra provide basic information about the structure of the polymer film. A typical spectrum is shown in the accompanying figure. The position of the first peak is related to the polymer chain length and resolved multiple vibronic peaks are an indication of film structure and morphology. We will also present results related to the optical degradation of these materials when exposed to air and UV light

  7. Structure–property relationships of electroluminescent polythiophenes

    Indian Academy of Sciences (India)

    A series of conjugated polythiophenes containing nitrogen-containing heterocycles as side chain, with differing substituent nature and linkage have been studied using quantum-chemical calculations. The optical properties of synthesized polymers were compared with that of model compounds with intricate structural ...

  8. Novel electrical transport properties in conducting polymers such as polythiophene and Poly(3-Methylthiophene)

    International Nuclear Information System (INIS)

    Kazama, Shigeo; Masubuchi, Shin-ichi; Matsuyama, Tomochika; Matsushita, Rokuji.

    1994-01-01

    Electric transport properties in most of the conducting organic polymers have provided a riddle that prevents a thorough physical understanding of the conduction mechanism. Major difficulties for approaching the most substantial aspect in the electrical transport properties underlie in complicated higher order structure inherent to polymeric materials consisting of crystalline regions entangled with disordered amorphous regions. In order to clearly understand the origin of the metallic nature of conducting polymers, we have to extract the proper transport properties characteristics of the ordered crystalline regions. We have made a series of experimental studies of the transport properties in conductive polythiophene and poly(3-methylthiophene) obtained with the electrochemical polymerization. For polythiophene, we have investigated both the as-grown samples and the ones that contain controlled amount of dopant species exchanged after the neutralization aiming to see the effect of dopant concentration on the transport properties. (author)

  9. Characteristics of Electro-Optic Device Using Conducting Polymers, Polythiophene and Polypyrrole Films

    Science.gov (United States)

    Kaneto, Keiichi; Yoshino, Katsumi; Inuishi, Yoshio

    1983-07-01

    Detailed characteristics of electro-optic elements (color switching and memory) utilizing the spectral change of conducting polymers by electrochemical doping and undoping are studied. The response time of color switching, for example, red≤ftrightarrowblue in polythiophene film in the electrolyte of LiBF4/acetonitrile is 30˜100 msec under the applied voltages of -2.0{≤ftrightarrow}+4.0 V vs. Li plate. More than 103 cycles of color switch are observed quite reproducibly. Three color states of yellow green, dark brown and blue are demonstrated for polypyrrole film.

  10. Polythiophene-based conjugated polyelectrolyte: Optical properties and association behavior in solution

    Czech Academy of Sciences Publication Activity Database

    Urbánek, P.; di Martino, A.; Gladyš, S.; Kuřitka, I.; Minařík, A.; Pavlova, Ewa; Bondarev, D.

    2015-01-01

    Roč. 202, April (2015), s. 16-24 ISSN 0379-6779 R&D Projects: GA TA ČR(CZ) TE01020118; GA ČR GAP108/12/1143 Institutional support: RVO:61389013 Keywords : polyelectrolyte * conjugated polymer * UV–vis spectroscopy Subject RIV: CD - Macromolecular Chemistry Impact factor: 2.299, year: 2015

  11. Conjugated polymer nanoparticles, methods of using, and methods of making

    KAUST Repository

    Habuchi, Satoshi

    2017-03-16

    Embodiments of the present disclosure provide for conjugated polymer nanoparticle, method of making conjugated polymer nanoparticles, method of using conjugated polymer nanoparticle, polymers, and the like.

  12. Conjugated polymer nanoparticles, methods of using, and methods of making

    KAUST Repository

    Habuchi, Satoshi; Piwonski, Hubert Marek; Michinobu, Tsuyoshi

    2017-01-01

    Embodiments of the present disclosure provide for conjugated polymer nanoparticle, method of making conjugated polymer nanoparticles, method of using conjugated polymer nanoparticle, polymers, and the like.

  13. Entanglements in Conjugated Polymers

    Science.gov (United States)

    Xie, Renxuan; Lee, Youngmin; Aplan, Melissa; Caggiano, Nick; Gomez, Enrique; Colby, Ralph

    Conjugated polymers, such as poly(3-hexylthiophene-2,5-diyl) (P3HT) and poly-((9,9-dioctylfluorene)-2,7-diyl-alt-[4,7-bis(thiophen-5-yl)-2,1,3-benzothiadiazole]-2',2''-diyl) (PFTBT), are widely used as hole and electron transport materials in a variety of electronic devices. However, fundamental knowledge regarding chain entanglements and nematic-to-isotropic transition is still lacking and are crucial to maximize charge transport properties. A systematic melt rheology study on P3HT with various molecular weights and regio regularities was performed. We find that the entanglement molecular weight Me is 5.0 kg/mol for regiorandom P3HT, but the apparent Me for regioregular P3HT is significantly higher. The difference is postulated to arise from the presence of a nematic phase only in regioregular P3HT. Analogously, PFTBT shows a clear rheological signature of the nematic-to-isotropic transition as a reversible sharp transition at 278 C. Shearing of this nematic phase leads to anisotropic crystalline order in PFTBT. We postulate that aligning the microstructure will impact charge transport and thereby advance the field of conducting polymers. National Science Foundation.

  14. Conjugated polymer zwitterions and solar cells comprising conjugated polymer zwitterions

    Science.gov (United States)

    Emrick, Todd; Russell, Thomas; Page, Zachariah; Liu, Yao

    2018-06-05

    A conjugated polymer zwitterion includes repeating units having structure (I), (II), or a combination thereof ##STR00001## wherein Ar is independently at each occurrence a divalent substituted or unsubstituted C3-30 arylene or heteroarylene group; L is independently at each occurrence a divalent C1-16 alkylene group, C6-30arylene or heteroarylene group, or alkylene oxide group; and R1 is independently at each occurrence a zwitterion. A polymer solar cell including the conjugated polymer zwitterion is also disclosed.

  15. Conformation Control of a Conjugated Polymer through Complexation with Bile Acids Generates Its Novel Spectral and Morphological Properties.

    Science.gov (United States)

    Tsuchiya, Youichi; Noguchi, Takao; Yoshihara, Daisuke; Roy, Bappaditya; Yamamoto, Tatsuhiro; Shinkai, Seiji

    2016-11-29

    Control of higher-order polymer structures attracts a great deal of interest for many researchers when they lead to the development of materials having various advanced functions. Among them, conjugated polymers that are useful as starting materials in the design of molecular wires are particularly attractive. However, an equilibrium existing between isolated chains and bundled aggregates is inevitable and has made their physical properties very complicated. As an attempt to simplify this situation, we previously reported that a polymer chain of a water-soluble polythiophene could be isolated through complexation with a helix-forming polysaccharide. More recently, a covalently self-threading polythiophene was reported, the main chain of which was physically protected from self-folding and chain-chain π-stacking. In this report, we wish to report a new strategy to isolate a water-soluble polythiophene and to control its higher-order structure by a supramolecular approach: that is, among a few bile acids, lithocholate can form stoichiometric complexes with cationic polythiophene to isolate the polymer chain, and the higher-order structure is changeable by the molar ratio. The optical and morphological studies have been thoroughly performed, and the resultant complex has been applied to the selective recognition of two AMP structural isomers.

  16. Conjugated Polymers for Energy Production

    DEFF Research Database (Denmark)

    Livi, Francesco

    This dissertation is aimed at developing materials for flexible, large area, ITO-free polymer solar cells (PSCs) fully printed under ambient conditions. A large screening of conjugated polymers, both novel and well-known materials, has been carried out in order to find suitable candidates...... polymerization method for industrial production of polymers. Several DArP protocols have been employed for the synthesis of PPDTBT leading to polymers with high structural regularity and photovoltaic performances comparable with the same materials synthesized via Stille cross-coupling polymerization...

  17. Conjugated Polymer Solar Cells

    Science.gov (United States)

    2006-05-01

    thermal gravimetry analysis (TGA)............... 12 2.6 Photoluminescence (PL) spectroscopy... gravimetry analysis (TGA) Thermal analysis of polymer films has been accomplished by TGA and DSC methods with the aid of Perkin-Elmer Series 7 Analysers...The MEH-PPV/acceptor films were prepared by spin-casting of the resulting mixture (with or without precipitate ) on glass substrates of diameter 23 mm

  18. Subgap Absorption in Conjugated Polymers

    Science.gov (United States)

    Sinclair, M.; Seager, C. H.; McBranch, D.; Heeger, A. J; Baker, G. L.

    1991-01-01

    Along with X{sup (3)}, the magnitude of the optical absorption in the transparent window below the principal absorption edge is an important parameter which will ultimately determine the utility of conjugated polymers in active integrated optical devices. With an absorptance sensitivity of materials. We have used PDS to measure the optical absorption spectra of the conjugated polymers poly(1,4-phenylene-vinylene) (and derivitives) and polydiacetylene-4BCMU in the spectral region from 0.55 eV to 3 eV. Our spectra show that the shape of the absorption edge varies considerably from polymer to polymer, with polydiacetylene-4BCMU having the steepest absorption edge. The minimum absorption coefficients measured varied somewhat with sample age and quality, but were typically in the range 1 cm{sup {minus}1} to 10 cm{sup {minus}1}. In the region below 1 eV, overtones of C-H stretching modes were observed, indicating that further improvements in transparency in this spectral region might be achieved via deuteration of fluorination.

  19. Subgap absorption in conjugated polymers

    Energy Technology Data Exchange (ETDEWEB)

    Sinclair, M.; Seager, C.H. (Sandia National Labs., Albuquerque, NM (USA)); McBranch, D.; Heeger, A.J. (California Univ., Santa Barbara, CA (USA)); Baker, G.L. (Bell Communications Research, Inc., Red Bank, NJ (USA))

    1991-01-01

    Along with X{sup (3)}, the magnitude of the optical absorption in the transparent window below the principal absorption edge is an important parameter which will ultimately determine the utility of conjugated polymers in active integrated optical devices. With an absorptance sensitivity of < 10{sup {minus}5}, Photothermal Deflection Spectroscopy (PDS) is ideal for determining the absorption coefficients of thin films of transparent'' materials. We have used PDS to measure the optical absorption spectra of the conjugated polymers poly(1,4-phenylene-vinylene) (and derivitives) and polydiacetylene-4BCMU in the spectral region from 0.55 eV to 3 eV. Our spectra show that the shape of the absorption edge varies considerably from polymer to polymer, with polydiacetylene-4BCMU having the steepest absorption edge. The minimum absorption coefficients measured varied somewhat with sample age and quality, but were typically in the range 1 cm{sup {minus}1} to 10 cm{sup {minus}1}. In the region below 1 eV, overtones of C-H stretching modes were observed, indicating that further improvements in transparency in this spectral region might be achieved via deuteration of fluorination. 11 refs., 4 figs.

  20. Influence of processing and intrinsic polymer parameters on photochemical stability of polythiophene thin films

    DEFF Research Database (Denmark)

    Vesterager Madsen, Morten; Tromholt, Thomas; Böttiger, Arvid P.L.

    2012-01-01

    shielding effects were shown to have a negligible effect on the photochemical degradation rate. The results obtained in this work advance the understanding of polymer stability and will help improve the design of materials used for polymer solar cells resulting in longer lifetimes, which will push......Intrinsic polymer parameters such as regio-regularity, molecular weight, and crystallinity play an important role when studying polymer stability. 18 different batches of poly-3-hexyl-thiophene (P3HT) were degraded in a solar simulator (AM1.5G, 1000 W/m2) and the degradation kinetics were monitored....... The results suggest that the radical reaction responsible for the photodegradation takes place at terminal thiophene rings exposed at points were the conjugation is broken. This proposed mechanism is supported by the fact that stability scales with regio-regularity following the ratio of head...

  1. Conjugated polymers developed from alkynes

    Institute of Scientific and Technical Information of China (English)

    Yajing Liu; Jacky W.Y.Lam; Ben Zhong Tang

    2015-01-01

    The numerous merits of conjugated polymers(CPs) have encouraged scientists to develop a variety of synthetic routes to CPs with diverse structures and functionalities. Among the large scope of substrates,alkyne plays an important role in constructing polymers with conjugated backbones. In addition to some well-developed reactions including Glaser–Hay and Sonogashira coupling, azide/thiol-yne click reaction and cyclotrimerization, some novel alkyne-based reactions have also been explored such as oxidative polycoupling, decarbonylative polycoupling and multicomponent tandem polymerizations. his review focuses on the recent progress on the synthetic methodology of CPs in the last ive years using monomers with two or more triple bonds and some of their high-technological applications. Selected examples of materials properties of these CPs are given in this review, such as luorescence response to chemical or physical stimuli, magnetism, white light emission, cell imaging and bioprobing. Finally, a short perspective is raised in regard to the outlook of the preparation methodologies, functionalities as well as potential applications of CPs in the future.

  2. Synthesis and Exciton Dynamics of Triplet Sensitized Conjugated Polymers

    KAUST Repository

    Andernach, Rolf; Utzat, Hendrik; Dimitrov, Stoichko; McCulloch, Iain; Heeney, Martin; Durrant, James; Bronstein, Hugo

    2015-01-01

    We report the synthesis of a novel polythiophene-based host-guest copolymer incorporating a Pt-porphyrin complex (TTP-Pt) into the backbone for efficient singlet to triplet polymer exciton sensitization. We elucidated the exciton dynamics in thin

  3. Conjugated Polymers as Actuators: Modes of Actuation

    DEFF Research Database (Denmark)

    Skaarup, Steen

    2004-01-01

    The physical and chemical properties of conjugated polymers often depend very strongly on the degree of doping with anions or cations. The movement of ions in and out of the polymer matrix as it is redox cycled is also accompanied by mechanical changes. Both the volume and the stiffness can exhibit...... significant differences between the oxidized and reduced states. These effects form the basis of the use of conjugated polymers as actuators (or “artificial muscles”) controllable by a small (1-10 V) voltage. Three basic modes of actuation (bending, linear extension and stiffness change) have been proposed...

  4. Conjugated polymers as actuators: modes of actuation

    DEFF Research Database (Denmark)

    Skaarup, Steen

    2007-01-01

    The physical and chemical properties of conjugated polymers often depend very strongly on the degree of doping with anions or cations. The movement of ions in and out of the polymer matrix as it is redox cycled is also accompanied by mechanical changes. Both the volume and the stiffness can exhibit...... significant differences between the oxidized and reduced states. These effects form the basis of the use of conjugated polymers as actuators (or “artificial muscles”) controllable by a small (1-10 V) voltage. Three basic modes of actuation (bending, linear extension and stiffness change) have been proposed...

  5. Colloidal systems of silver nanoparticles and high-regioregular cationic polythiophene with ionic-liquid-like pendant groups: Optical properties and SERS

    Czech Academy of Sciences Publication Activity Database

    Kazim, Samrana; Pfleger, Jiří; Procházka, M.; Bondarev, D.; Vohlídal, J.

    2011-01-01

    Roč. 354, č. 2 (2011), s. 611-619 ISSN 0021-9797 R&D Projects: GA AV ČR KAN100500652; GA ČR GA203/07/0717 Institutional research plan: CEZ:AV0Z40500505 Keywords : ionic conjugated polymer * polythiophene polyelectrolyte * plasmonic nanoparticle Subject RIV: CD - Macromolecular Chemistry Impact factor: 3.070, year: 2011

  6. Conjugated polymer photovoltaic devices and materials

    International Nuclear Information System (INIS)

    Mozer, A.J.; Niyazi, Serdar Sariciftci

    2006-01-01

    The science and technology of conjugated polymer-based photovoltaic devices (bulk heterojunction solar cells) is highlighted focusing on three major issues, i.e. (i) nano-morphology optimization, (ii) improving charge carrier mobility, (iii) improving spectral sensitivity. Successful strategies towards improved photovoltaic performance are presented using various novel materials, including double-cable polymers, regioregular polymers and low bandgap polymers. The examples presented herein demonstrate that the bulk heterojunction concept is a viable approach towards developing photovoltaic systems by inexpensive solution-based fabrication technologies. (authors)

  7. Integrated circuits based on conjugated polymer monolayer.

    Science.gov (United States)

    Li, Mengmeng; Mangalore, Deepthi Kamath; Zhao, Jingbo; Carpenter, Joshua H; Yan, Hongping; Ade, Harald; Yan, He; Müllen, Klaus; Blom, Paul W M; Pisula, Wojciech; de Leeuw, Dago M; Asadi, Kamal

    2018-01-31

    It is still a great challenge to fabricate conjugated polymer monolayer field-effect transistors (PoM-FETs) due to intricate crystallization and film formation of conjugated polymers. Here we demonstrate PoM-FETs based on a single monolayer of a conjugated polymer. The resulting PoM-FETs are highly reproducible and exhibit charge carrier mobilities reaching 3 cm 2  V -1  s -1 . The high performance is attributed to the strong interactions of the polymer chains present already in solution leading to pronounced edge-on packing and well-defined microstructure in the monolayer. The high reproducibility enables the integration of discrete unipolar PoM-FETs into inverters and ring oscillators. Real logic functionality has been demonstrated by constructing a 15-bit code generator in which hundreds of self-assembled PoM-FETs are addressed simultaneously. Our results provide the state-of-the-art example of integrated circuits based on a conjugated polymer monolayer, opening prospective pathways for bottom-up organic electronics.

  8. Stable inverted polymer/fullerene solar cells using a cationic polythiophene modified PEDOT:PSS cathodic interface

    Energy Technology Data Exchange (ETDEWEB)

    Rider, David A.; Worfolk, Brian J.; Buriak, Jillian M. [Department of Chemistry, University of Alberta, Edmonton, Alberta (Canada); NRC National Institute for Nanotechnology, Edmonton, Alberta (Canada); Harris, Kenneth D.; Shahbazi, Kevin; Fleischauer, Michael D. [NRC National Institute for Nanotechnology, Edmonton, Alberta (Canada); Lalany, Abeed [Department of Electrical and Computer Engineering, University of Alberta, Edmonton (Canada); Brett, Michael J. [NRC National Institute for Nanotechnology, Edmonton, Alberta (Canada); Department of Electrical and Computer Engineering, University of Alberta, Edmonton (Canada)

    2010-08-09

    A cationic and water-soluble polythiophene [poly[3-(6-pyridiniumylhexyl)thiophene bromide](P3PHT{sup +}Br{sup -})] is synthesized and used in combination with anionic poly(3,4-ethylenedioxythiophene):poly(p-styrenesulfonate) (PEDOT:PSS){sup -} to produce hybrid coatings on indium tin oxide (ITO). Two coating strategies are established: i) electrostatic layer-by-layer assembly with colloidal suspensions of (PEDOT:PSS){sup -}, and ii) modification of an electrochemically prepared (PEDOT:PSS){sup -} film on ITO. The coatings are found to modify the work function of ITO such that it could act as a cathode in inverted 2,5-diyl-poly(3-hexylthiophene) (P3HT)/[6,6]-phenyl-C{sub 61}-butyric acid methyl ester (PCBM) polymer photovoltaic cells. The interfacial modifier created from the layer-by-layer assembly route is used to produce efficient inverted organic photovoltaic devices (power conversion efficiency {proportional_to}2%) with significant long-term stability in excess of 500 h. (Abstract Copyright [2010], Wiley Periodicals, Inc.)

  9. Compositions for directed alignment of conjugated polymers

    Science.gov (United States)

    Kim, Jinsang; Kim, Bong-Gi; Jeong, Eun Jeong

    2016-04-19

    Conjugated polymers (CPs) achieve directed alignment along an applied flow field and a dichroic ratio of as high as 16.67 in emission from well-aligned thin films and fully realized anisotropic optoelectronic properties of CPs in field-effect transistor (FET).

  10. Conjugated Polymer Actuators: Prospects and Limitations

    DEFF Research Database (Denmark)

    Skaarup, Steen

    2007-01-01

    Actuators constructed with a conjugated polymer as the active part have been predicted to have a number of highly desirable properties: Large mechanical strength, high power density, i.e. high actuation speeds possible, sufficient maximum strain values, high reversibility and safe, low voltages (1...

  11. Optical rotation and electron spin resonance of an electro-optically active polythiophene

    International Nuclear Information System (INIS)

    Goto, Hiromasa

    2010-01-01

    Graphical abstract: The electro-chiroptical polythiophene displays optical rotation at wavelengths corresponding to the doping band observable in the absorption spectra. The formation of polarons on the main-chain is confirmed by electron spin resonance measurements. - Abstract: A chiroptical polythiophene, is synthesized by electrolytic polymerization in a cholesteric liquid crystal electrolyte solution. The polymer displays a fingerprint texture similar to that of the cholesteric electrolyte solution. Upon electrochemical doping, the polymer displays optical rotation at wavelengths corresponding to the doping band observable in the absorption spectra. The formation of polarons on the main-chain is confirmed by electron spin resonance measurements. The results demonstrate the intermolecular chirality of polarons in this π-conjugated polymer, indicating continuum delocalized polarons are in a three-dimensional helical environment.

  12. Conjugated Polymers Atypically Prepared in Water

    Science.gov (United States)

    Invernale, Michael A.; Pendergraph, Samuel A.; Yavuz, Mustafa S.; Ombaba, Matthew; Sotzing, Gregory A.

    2010-01-01

    Processability remains a fundamental issue for the implementation of conducting polymer technology. A simple synthetic route towards processable precursors to conducting polymers (main chain and side chain) was developed using commercially available materials. These soluble precursor systems were converted to conjugated polymers electrochemically in aqueous media, offering a cheaper and greener method of processing. Oxidative conversion in aqueous and organic media each produced equivalent electrochromics. The precursor method enhances the yield of the electrochromic polymer obtained over that of electrodeposition, and it relies on a less corruptible electrolyte bath. However, electrochemical conversion of the precursor polymers often relies on organic salts and solvents. The ability to achieve oxidative conversion in brine offers a less costly and a more environmentally friendly processing step. It is also beneficial for biological applications. The electrochromics obtained herein were evaluated for electronic, spectral, and morphological properties. PMID:20959869

  13. Analytical characterization of polymer-drug conjugates

    International Nuclear Information System (INIS)

    Rizzo, V.; Gigli, M.; Pinciroli, V.

    1998-01-01

    A few polymeric conjugates of antitumor drugs have been recently developed in view of possible therapeutic advantages: solubilization of sparingly soluble drugs in water, improvement of therapeutic index, organ targeting through a second chemical species bound to the same polymeric chain. In this article it's described the analytical approach used in the characterization of the conjugates for chemical identity, purity and strength of the contained active ingredient. The techniques are: high field NMR and size exclusion chromatography with non-aqueous mobile phase for identity; selective hydrolysis and HPLC for strength and purity. A complete and reliable picture is thus obtained both for qualitative and for quantitative aspects. This is an important step forward in the direction of further development and marketing of polymer-drug conjugates [it

  14. Bis-polymer lipid-peptide conjugates and nanoparticles thereof

    Energy Technology Data Exchange (ETDEWEB)

    Xu, Ting; Dong, He; Shu, Jessica; Dube, Nikhil

    2018-04-24

    The present invention provides bis-polymer lipid-peptide conjugates containing a hydrophobic block and headgroup containing a helical peptide and two polymer blocks. The conjugates can self-assemble to form helix bundle subunits, which in turn assemble to provide micellar nanocarriers for drug cargos and other agents. Particles containing the conjugates and methods for forming the particles are also disclosed.

  15. Side Chain Engineering in Solution-Processable Conjugated Polymers

    KAUST Repository

    Mei, Jianguo; Bao, Zhenan

    2014-01-01

    Side chains in conjugated polymers have been primarily utilized as solubilizing groups. However, these side chains have roles that are far beyond. We advocate using side chain engineering to tune a polymer's physical properties, including absorption

  16. Electrostimulated Release of Neutral Drugs from Polythiophene Nanoparticles: Smart Regulation of Drug-Polymer Interactions.

    Science.gov (United States)

    Puiggalí-Jou, Anna; Micheletti, Paolo; Estrany, Francesc; Del Valle, Luis J; Alemán, Carlos

    2017-09-01

    Poly(3,4-ethylenedioxythiophene) (PEDOT) nanoparticles are loaded with curcumin and piperine by in situ emulsion polymerization using dodecyl benzene sulfonic acid both as a stabilizer and a doping agent. The loaded drugs affect the morphology, size, and colloidal stability of the nanoparticles. Furthermore, kinetics studies of nonstimulated drug release have evidenced that polymer···drug interactions are stronger for curcumin than for piperine. This observation suggests that drug delivery systems based on combination of the former drug with PEDOT are much appropriated to show an externally tailored release profile. This is demonstrated by comparing the release profiles obtained in presence and absence of electrical stimulus. Results indicate that controlled and time-programmed release of curcumin is achieved in a physiological medium by applying a negative voltage of -1.25 V to loaded PEDOT nanoparticles. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. Synthesis and Exciton Dynamics of Triplet Sensitized Conjugated Polymers

    KAUST Repository

    Andernach, Rolf

    2015-07-22

    We report the synthesis of a novel polythiophene-based host-guest copolymer incorporating a Pt-porphyrin complex (TTP-Pt) into the backbone for efficient singlet to triplet polymer exciton sensitization. We elucidated the exciton dynamics in thin films of the material by means of Transient Absorption Spectrosopcy (TAS) on multiple timescales and investigated the mechanism of triplet exciton formation. During sensitization, single exciton diffusion is followed by exciton transfer from the polymer backbone to the complex where it undergoes intersystem crossing to the triplet state of the complex. We directly monitored the triplet exciton back transfer from the Pt-porphyrin to the polymer and find that 60% of the complex triplet excitons are transferred with a time constant of 1087 ps. We propose an equilibrium between polymer and porphyrin triplet states as a result of the low triplet diffusion length in the polymer backbone and hence an increased local triplet population resulting in increased triplet-triplet annihilation. This novel system has significant implications for the design of novel materials for triplet sensitized solar cells and up-conversion layers.

  18. Conjugated Polymers for Flexible Energy Harvesting and Storage.

    Science.gov (United States)

    Zhang, Zhitao; Liao, Meng; Lou, Huiqing; Hu, Yajie; Sun, Xuemei; Peng, Huisheng

    2018-03-01

    Since the discovery of conjugated polymers in the 1970s, they have attracted considerable interest in light of their advantages of having a tunable bandgap, high electroactivity, high flexibility, and good processability compared to inorganic conducting materials. The above combined advantages make them promising for effective energy harvesting and storage, which have been widely studied in recent decades. Herein, the key advancements in the use of conjugated polymers for flexible energy harvesting and storage are reviewed. The synthesis, structure, and properties of conjugated polymers are first summarized. Then, their applications in flexible polymer solar cells, thermoelectric generators, supercapacitors, and lithium-ion batteries are described. The remaining challenges are then discussed to highlight the future direction in the development of conjugated polymers. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. Recent Advances in Conjugated Polymers for Light Emitting Devices

    Science.gov (United States)

    AlSalhi, Mohamad Saleh; Alam, Javed; Dass, Lawrence Arockiasamy; Raja, Mohan

    2011-01-01

    A recent advance in the field of light emitting polymers has been the discovery of electroluminescent conjugated polymers, that is, kind of fluorescent polymers that emit light when excited by the flow of an electric current. These new generation fluorescent materials may now challenge the domination by inorganic semiconductor materials of the commercial market in light-emitting devices such as light-emitting diodes (LED) and polymer laser devices. This review provides information on unique properties of conjugated polymers and how they have been optimized to generate these properties. The review is organized in three sections focusing on the major advances in light emitting materials, recent literature survey and understanding the desirable properties as well as modern solid state lighting and displays. Recently, developed conjugated polymers are also functioning as roll-up displays for computers and mobile phones, flexible solar panels for power portable equipment as well as organic light emitting diodes in displays, in which television screens, luminous traffic, information signs, and light-emitting wallpaper in homes are also expected to broaden the use of conjugated polymers as light emitting polymers. The purpose of this review paper is to examine conjugated polymers in light emitting diodes (LEDs) in addition to organic solid state laser. Furthermore, since conjugated polymers have been approved as light-emitting organic materials similar to inorganic semiconductors, it is clear to motivate these organic light-emitting devices (OLEDs) and organic lasers for modern lighting in terms of energy saving ability. In addition, future aspects of conjugated polymers in LEDs were also highlighted in this review. PMID:21673938

  20. Nanostructured conjugated polymers in chemical sensors: synthesis, properties and applications.

    Science.gov (United States)

    Correa, D S; Medeiros, E S; Oliveira, J E; Paterno, L G; Mattoso, Luiz C

    2014-09-01

    Conjugated polymers are organic materials endowed with a π-electron conjugation along the polymer backbone that present appealing electrical and optical properties for technological applications. By using conjugated polymeric materials in the nanoscale, such properties can be further enhanced. In addition, the use of nanostructured materials makes possible miniaturize devices at the micro/nano scale. The applications of conjugated nanostructured polymers include sensors, actuators, flexible displays, discrete electronic devices, and smart fabric, to name a few. In particular, the use of conjugated polymers in chemical and biological sensors is made feasible owning to their sensitivity to the physicochemical conditions of its surrounding environment, such as chemical composition, pH, dielectric constant, humidity or even temperature. Subtle changes in these conditions bring about variations on the electrical (resistivity and capacitance), optical (absorptivity, luminescence, etc.), and mechanical properties of the conjugated polymer, which can be precisely measured by different experimental methods and ultimately associated with a specific analyte and its concentration. The present review article highlights the main features of conjugated polymers that make them suitable for chemical sensors. An especial emphasis is given to nanostructured sensors systems, which present high sensitivity and selectivity, and find application in beverage and food quality control, pharmaceutical industries, medical diagnosis, environmental monitoring, and homeland security, and other applications as discussed throughout this review.

  1. Conjugated Polymers and Oligomers: Structural and Soft Matter Aspects

    DEFF Research Database (Denmark)

    This book identifies modern topics and current trends of structural and soft matter aspects of conjugated polymers and oligomers. Each chapter recognizes an active research line where structural perspective dominates research and therefore the book covers fundamental aspects of persistent...

  2. Side Chain Engineering in Solution-Processable Conjugated Polymers

    KAUST Repository

    Mei, Jianguo

    2014-01-14

    Side chains in conjugated polymers have been primarily utilized as solubilizing groups. However, these side chains have roles that are far beyond. We advocate using side chain engineering to tune a polymer\\'s physical properties, including absorption, emission, energy level, molecular packing, and charge transport. To date, numerous flexible substituents suitable for constructing side chains have been reported. In this Perspective article, we advocate that the side chain engineering approach can advance better designs for next-generation conjugated polymers. © 2013 American Chemical Society.

  3. Structural and thermal properties of carboxylic acid functionalized polythiophenes

    Directory of Open Access Journals (Sweden)

    Ariane de França Mescoloto

    2014-01-01

    Full Text Available Polythiophenes functionalized with polar groups at the end of side-chain have emerged as an alternative method to obtain good compatibility between this class of conjugated polymers and electron acceptor compounds. The aim is to prevent phase segregation and to improve the efficiency of the polythiophene technological devices. However, homopolymers synthesized from thiophene rings with high polar groups at the end of the side-chain, such as hydroxyl and carboxylic acid groups, are poorly soluble in common volatile organic solvents. We report on a systematic preparation of copolymers of 3-hexylthiophene (HT and thiophene-3-acetic acid (TAA, using different feed ratios. The chemical structures of the copolymers were confirmed by FTIR and ¹H-NMR. The TAA content in these copolymers were 33, 38 and 54 mol %. HPSEC results did not show any remarkable correlation with TAA contents in the copolymers. In contrast, the thermal analyses showed a decrease in the thermal stability and an increase in rigidity of their backbones, for the copolymers with high amounts of TAA. The solubility and optical property of copolymers were also related to the TAA contents. Thus, the properties of these copolymers can be modulated by a simple control of feed ratio of TAA in the copolymerization.

  4. Difluorobenzothiadiazole based two-dimensional conjugated polymers with triphenylamine substituted moieties as pendants for bulk heterojunction solar cells

    Directory of Open Access Journals (Sweden)

    W. H. Lee

    2017-11-01

    Full Text Available Three donor/acceptor (D/A-type two-dimensional polythiophenes (PTs; PBTFA13, PBTFA12, PBTFA11 featuring difluorobenzothiadiazole (DFBT derivatives as the conjugated (acceptor units in the polymer backbone and tertbutyl–substituted triphenylamine (tTPA-containing moieties as (donor pendants have been synthesized and characterized. These PTs exhibited good thermal stabilities, broad absorption spectra, and narrow optical band gaps. The cutoff wavelength of the UV–Vis absorption band was red-shifted upon increasing the content of the DFBT units in the PTs. Bulk heterojunction solar cells having an active layer comprising blends of the PTs and fullerene derivatives [6,6] phenyl-C61/71-butyric acid methyl ester (PC61BM/PC71BM were fabricated; their photovoltaic performance was strongly dependent on the content of the DFBT derivative in the PT. Incorporating a suitable content of the DFBT derivative in the polymer backbone enhanced the solar absorption ability and conjugation length of the PTs. The photovoltaic properties of the PBTFA13-based solar cells were superior to those of the PBTFA11- and PBTFA12-based solar cells.

  5. Solvent-resistant organic transistors and thermally stable organic photovoltaics based on cross-linkable conjugated polymers

    KAUST Repository

    Kim, Hyeongjun

    2012-01-10

    Conjugated polymers, in general, are unstable when exposed to air, solvent, or thermal treatment, and these challenges limit their practical applications. Therefore, it is of great importance to develop new materials or methodologies that can enable organic electronics with air stability, solvent resistance, and thermal stability. Herein, we have developed a simple but powerful approach to achieve solvent-resistant and thermally stable organic electronic devices with a remarkably improved air stability, by introducing an azide cross-linkable group into a conjugated polymer. To demonstrate this concept, we have synthesized polythiophene with azide groups attached to end of the alkyl chain (P3HT-azide). Photo-cross-linking of P3HT-azide copolymers dramatically improves the solvent resistance of the active layer without disrupting the molecular ordering and charge transport. This is the first demonstration of solvent-resistant organic transistors. Furthermore, the bulk-heterojunction organic photovoltaics (BHJ OPVs) containing P3HT-azide copolymers show an average efficiency higher than 3.3% after 40 h annealing at an elevated temperature of 150 °C, which represents one of the most thermally stable OPV devices reported to date. This enhanced stability is due to an in situ compatibilizer that forms at the P3HT/PCBM interface and suppresses macrophase separation. Our approach paves a way toward organic electronics with robust and stable operations. © 2011 American Chemical Society.

  6. Identification of excited states in conjugated polymers

    International Nuclear Information System (INIS)

    Hartwell, Lewis John

    2003-01-01

    This thesis reports quasi steady state photoinduced absorption measurements from three conjugated polymers: polypyridine (PPy), polyfluorene (PFO) and the emeraldine base (EB) form of polyaniline. The aim of these experiments was to determine the nature of the photoexcited states existing in these materials in the millisecond time domain, as this has important consequences for the operation of real devices manufactured using these materials. The results from the photoinduced absorption experiments are closely compared with published results from pulse radiolysis experiments. In all cases there is very good correspondence between the two data sets, which has enabled the photoexcited states to be assigned with a high degree of confidence. Quasi steady-state photoinduced absorption involves the measurement of the change in absorption of a material in response to optical excitation with a laser beam. The changes in absorption are small, so a dedicated instrument was developed and optimised for each different sample. Lock-in techniques were used to recover the small signals from the samples. The samples involved were thin films of the polymer spin coated onto sapphire substrates in the cases of PPy and EB. Solution state experiments were conducted on EB. The experiments on PFO were conducted on aligned and unaligned thin films provided by Sony. In the case of the aligned PFO samples, the photoinduced absorption spectrometer was modified to enable polarisation-sensitive data collection. In PPy, both triplet excitons and polarons have been shown to be long-lived photoexcitations, with photoinduced absorption features at 2.29 eV (triplet exciton transition), 1.5 eV and 0.8 eV (polaron transitions). In PFO, the one observed photoinduced band at 1.52 eV is assigned to a triplet exciton. Two photoinduced absorption bands are observed in EB, at 1.4 eV and 0.8 eV. These are assigned to a self-trapped CT singlet exciton and triplet exciton, respectively. (author)

  7. Microfluidic Fabrication of Conjugated Polymer Sensor Fibers

    Energy Technology Data Exchange (ETDEWEB)

    Yoo, Imsung; Song, Simon [Hanyang University, Seoul (Korea, Republic of)

    2014-10-15

    We propose a fabrication method for polydiacetylene (PDA)-embedded hydrogel microfibers on a microfluidic chip. These fibers can be applied to the detection of cyclodextrines (CDs), which are a family of sugar and aluminum ions. PDA, a family of conjugated polymers, has unique characteristics when used for a sensor, because it undergoes a blue-to-red color transition and nonfluorescence-to-fluorescence transition in response to environmental stimulation. PDAs have different sensing characteristics depending on the head group of PCDA. By taking advantage of ionic crosslinking-induced hydrogel formation and the 3D hydrodynamic focusing effect on a microfluidic chip, PCDA-EDEA-derived diacetylene (DA) monomer-embedded microfibers were successfully fabricated. UV irradiation of the fibers afforded blue-colored PDA, and the resulting blue PDA fibers underwent a phase transition to red and emitted red fluorescence upon exposure to CDs and aluminum ions. Their fluorescence intensity varied depending on the CDs and aluminum ion concentrations. This phase transition was also observed when the fibers were dried.

  8. Lipid-peptide-polymer conjugates and nanoparticles thereof

    Science.gov (United States)

    Xu, Ting; Dong, He; Shu, Jessica

    2015-06-02

    The present invention provides a conjugate having a peptide with from about 10 to about 100 amino acids, wherein the peptide adopts a helical structure. The conjugate also includes a first polymer covalently linked to the peptide, and a hydrophobic moiety covalently linked to the N-terminus of the peptide, wherein the hydrophobic moiety comprises a second polymer or a lipid moiety. The present invention also provides helix bundles form by self-assembling the conjugates, and particles formed by self-assembling the helix bundles. Methods of preparing the helix bundles and particles are also provided.

  9. Incorporation of fused tetrathiafulvalenes (TTFs) into polythiophene architectures: varying the electroactive dominance of the TTF species in hybrid systems.

    Science.gov (United States)

    Berridge, Rory; Skabara, Peter J; Pozo-Gonzalo, Cristina; Kanibolotsky, Alexander; Lohr, Jan; McDouall, Joseph J W; McInnes, Eric J L; Wolowska, Joanna; Winder, Christoph; Sariciftci, N Serdar; Harrington, Ross W; Clegg, William

    2006-02-23

    A novel polythienylenevinylene (PTV) and two new polythiophenes (PTs), featuring fused tetrathiafulvalene (TTF) units, have been prepared and characterized by ultraviolet-visible (UV-vis) and electron paramagnetic resonance (EPR) spectroelectrochemistry. All polymers undergo two sequential, reversible oxidation processes in solution. Structures in which the TTF species is directly linked to the polymer backbone (2 and 4) display redox behavior which is dictated by the fulvalene system. Once the TTF is spatially removed from the polymer chain by a nonconjugated link (polymer 3), the electroactivity of both TTF and polythiophene moieties can be detected. Computational studies confirm the delocalization of charge over both electroactive centers (TTF and PT) and the existence of a triplet dication intermediate. PTV 4 has a low band gap (1.44 eV), is soluble in common organic solvents, and is stable under ambient conditions. Organic solar cells of polymer 4:[6,6]-phenyl-C(61) butyric acid methyl ester (PCBM) have been fabricated. Under illumination, a photovoltaic effect is observed with a power conversion efficiency of 0.13% under AM1.5 solar simulated light. The onset of photocurrent at 850 nm is consistent with the onset of the pi-pi absorption band of the polymer. Remarkably, UV-vis spectroelectrochemistry of polymer 4 reveals that the conjugated polymer chain remains unchanged during the oxidation of the polymer.

  10. Synthesis of regioregular pentacene-containing conjugated polymers

    KAUST Repository

    Okamoto, Toshihiro; Jiang, Ying; Becerril, Hector A.; Hong, Sanghyun; Senatore, Michelle L.; Tang, Ming L.; Toney, Michael F.; Siegrist, Theo; Bao, Zhenan

    2011-01-01

    We report the synthesis and characterization of a new class of regioregular pentacene-containing conjugated polymers via our synthetic routes reported previously. We found that our regioregular pentacene polymers showed improved ordering than their regiorandom counterpart as well as ambipolar OFET performance. © 2011 The Royal Society of Chemistry.

  11. Preparation of conjugated polymer suspensions by using ultrasonic atomizer

    Energy Technology Data Exchange (ETDEWEB)

    Tada, Kazuya, E-mail: tada@eng.u-hyogo.ac.jp; Onoda, Mitsuyoshi

    2010-11-30

    The electrophoretic deposition is a method useful to prepare conjugated polymer films for electronic devices. This method provides high material recovery rate on the substrate from the suspension, in contrast to the conventional spin-coating in which most of the material placed on the substrate is blown away. Although manual reprecipitation technique successfully yields suspensions of various conjugated polymers including polyfluorene derivatives, it is favorable to control the preparation process of suspensions. In this context, this paper reports preliminary results on the preparation of suspension of conjugated polymer by using an ultrasonic atomizer. While the resultant films do not show particular difference due to the preparation methods of the suspension, the electric current profiles during the electrophoretic deposition suggests that the ultrasonic atomization of polymer solution prior to be mixed with poor solvent results in smaller and less uniform colloidal particles than the conventional manual pouring method.

  12. Synthesis and study of conjugated polymers containing Di- or Triphenylamine

    Energy Technology Data Exchange (ETDEWEB)

    Sukwattanasinitt, M.

    1996-06-21

    This thesis consists of two separate parts. The first part addresses the synthesis and study of conjugated polymers containing di- or triphenylamine. Two types of polymers: linear polymers and dendrimers, were synthesized. The polymers were characterized by NMR, IR, UV, GPC, TGA and DSC. Electronic and optical properties of the polymers were studied through the conductivity measurements and excitation- emission spectra. the second part of this thesis deals with a reaction of electron-rich acetylenes with TCNE. The discovery of the reaction from charge transfer complex studies and the investigation of this reaction on various electron-rich acetylenes are presented.

  13. Dye linked conjugated homopolymers: using conjugated polymer electroluminescence to optically pump porphyrin-dye emission

    DEFF Research Database (Denmark)

    Nielsen, K.T.; Spanggaard, H.; Krebs, Frederik C

    2004-01-01

    . Electroluminescent devices of the homopolymer itself and of the zinc-porphyrin containing polymer were prepared and the nature of the electroluminescence was characterized. The homopolymer segments were found to optically pump the emission of the zinc-porphyrin dye moities. The homopolymer exhibits blue......Zinc-porphyrin dye molecules were incorporated into the backbone of a conjugated polymer material by a method, which allowed for the incorporation of only one zinc-porphyrin dye molecule into the backbone of each conjugated polymer molecule. The electronic properties of the homopolymer were...

  14. Soluble polymer conjugates for drug delivery.

    Science.gov (United States)

    Minko, Tamara

    2005-01-01

    The use of water-soluble polymeric conjugates as drug carriers offers several possible advantages. These advantages include: (1) improved drug pharmacokinetics; (2) decreased toxicity to healthy organs; (3) possible facilitation of accumulation and preferential uptake by targeted cells; (4) programmed profile of drug release. In this review, we will consider the main types of useful polymeric conjugates and their role and effectiveness as carriers in drug delivery systems.: © 2005 Elsevier Ltd . All rights reserved.

  15. Conformation-related exciton localization and charge-pair formation in polythiophenes: ensemble and single-molecule study.

    Science.gov (United States)

    Sugimoto, Toshikazu; Habuchi, Satoshi; Ogino, Kenji; Vacha, Martin

    2009-09-10

    We study conformation-dependent photophysical properties of polythiophene (PT) by molecular dynamics simulations and by ensemble and single-molecule optical experiments. We use a graft copolymer consisting of a polythiophene backbone and long polystyrene branches and compare its properties with those obtained on the same polythiophene derivative without the side chains. Coarse-grain molecular dynamics simulations show that in a poor solvent, the PT without the side chains (PT-R) forms a globulelike conformation in which distances between any two conjugated segments on the chain are within the Forster radius for efficient energy transfer. In the PT with the polystyrene branches (PT-PS), the polymer main PT chain retains an extended coillike conformation, even in a poor solvent, and the calculated distances between conjugated segments favor energy transfer only between a few neighboring chromophores. The theoretical predictions are confirmed by measurements of fluorescence anisotropy and fluorescence blinking of the polymers' single chains. High anisotropy ratios and two-state blinking in PT-R are due to localization of the exciton on a single conjugated segment. These signatures of exciton localization are absent in single chains of PT-PS. Electric-field-induced quenching measured as a function of concentration of PT dispersed in an inert matrix showed that in well-isolated chains of PT-PS, the exciton dissociation is an intrachain process and that aggregation of the PT-R chains causes an increase in quenching due to the onset of interchain interactions. Measurements of the field-induced quenching on single chains indicate that in PT-R, the exciton dissociation is a slower process that takes place only after the exciton is localized on one conjugated segment.

  16. Excitons in conjugated polymers: Do we need a paradigma change?

    Energy Technology Data Exchange (ETDEWEB)

    Beenken, Wichard J.D. [Department of Theoretical Physics I, Ilmenau University of Thechnology (Germany)

    2009-12-15

    We have previously shown that both, polymer conformation and dynamics are crucial for the exciton transport in conjugated polymers. Thereby we found that the usual Foerster-type hopping transfer model - even if one applies the line-dipole approximation - falls short in one crucial aspect: the nature of the sites the excitons are transferred between is still unclear. We found that the simple model of spectroscopic units defined as segments of the polymer chains separated by structural defects breaking the {pi}-conjugation is only justified for chemical defects like hydrogenated double bonds, or extreme gauche (90 ) torsions between the monomers. Both defects are far too rare in a well-prepared conjugated polymer to explain the mean spectroscopic-unit length of typically 6-7 monomers. Meanwhile, also the concept of dynamical formation of the spectroscopic units, we had previously suggested, has also failed. Thus the question of a paradigma change concerning the exciton transport in conjugated polymers appears on the agenda. (Abstract Copyright [2009], Wiley Periodicals, Inc.)

  17. Realization of large area flexible fullerene - conjugated polymer photocells: a route to plastic solar cells

    NARCIS (Netherlands)

    Brabec, C.J.; Padinger, F.; Hummelen, J.C.; Janssen, R.A.J.; Sariciftci, N.S.

    1999-01-01

    Bulk donor — acceptor heterojunctions between conjugated polymers and fullerenes have been utilized for photovoltaic devices with quantum efficiencies of around 1%. These devices are based on the photoinduced, ultrafast electron transfer between non degenerate ground state conjugated polymers and

  18. Non-classical light emission from single conjugated polymers

    Science.gov (United States)

    Hollars, Christopher; Lane, Stephen; Huser, Thomas

    2002-03-01

    Photon-antibunching from single, isolated molecules of collapsed-chain poly[2-methoxy,5-(2’-ethyl-hexyloxy)-p-phenylene-vinylene] (MEH-PPV) has been observed using confocal microscopy techniques. Efficient inter-segment energy transfer in collapsed-chain conjugated polymers leads to emission from an average of only 2-3 active sites on a polymer chain that is composed of hundreds of quasi-chromophores. These few centers consist of the segments with the lowest excitation energy and are supplied by the efficient light-harvesting and energy transfer of the surrounding higher-energy segments. This effect depends on the conformation of the polymer molecules, which is controlled by solvent polarity. These results provide new insight into the controversial photophysics of conjugated polymers and their application in optoelectronic devices.

  19. Exploring the origin of high optical absorption in conjugated polymers

    KAUST Repository

    Vezie, Michelle S.

    2016-05-16

    The specific optical absorption of an organic semiconductor is critical to the performance of organic optoelectronic devices. For example, higher light-harvesting efficiency can lead to higher photocurrent in solar cells that are limited by sub-optimal electrical transport. Here, we compare over 40 conjugated polymers, and find that many different chemical structures share an apparent maximum in their extinction coefficients. However, a diketopyrrolopyrrole-thienothiophene copolymer shows remarkably high optical absorption at relatively low photon energies. By investigating its backbone structure and conformation with measurements and quantum chemical calculations, we find that the high optical absorption can be explained by the high persistence length of the polymer. Accordingly, we demonstrate high absorption in other polymers with high theoretical persistence length. Visible light harvesting may be enhanced in other conjugated polymers through judicious design of the structure.

  20. Exploring the origin of high optical absorption in conjugated polymers

    KAUST Repository

    Vezie, Michelle S.; Few, Sheridan; Meager, Iain; Pieridou, Galatia; Dö rling, Bernhard; Ashraf, Raja Shahid; Goñ i, Alejandro R.; Bronstein, Hugo; McCulloch, Iain; Hayes, Sophia C.; Campoy-Quiles, Mariano; Nelson, Jenny

    2016-01-01

    The specific optical absorption of an organic semiconductor is critical to the performance of organic optoelectronic devices. For example, higher light-harvesting efficiency can lead to higher photocurrent in solar cells that are limited by sub-optimal electrical transport. Here, we compare over 40 conjugated polymers, and find that many different chemical structures share an apparent maximum in their extinction coefficients. However, a diketopyrrolopyrrole-thienothiophene copolymer shows remarkably high optical absorption at relatively low photon energies. By investigating its backbone structure and conformation with measurements and quantum chemical calculations, we find that the high optical absorption can be explained by the high persistence length of the polymer. Accordingly, we demonstrate high absorption in other polymers with high theoretical persistence length. Visible light harvesting may be enhanced in other conjugated polymers through judicious design of the structure.

  1. Hybrid zinc oxide conjugated polymer bulk heterojunction solar cells

    NARCIS (Netherlands)

    Beek, W.J.E.; Wienk, M.M.; Kemerink, M.; Yang, X.N.; Janssen, R.A.J.

    2005-01-01

    Bulk heterojunction photovoltaic devices based on blends of a conjugated polymer poly[2-methoxy-5-(3‘,7‘-dimethyloctyloxy)-1,4-phenylenevinylene] (MDMO-PPV) as electron donor and crystalline ZnO nanoparticles (nc-ZnO) as electron acceptor have been studied. Composite nc-ZnO:MDMO-PPV films were cast

  2. Scanning-tunneling spectroscopy on conjugated polymer films

    NARCIS (Netherlands)

    Kemerink, M.; Alvarado, S.F.; Koenraad, P.M.; Janssen, R.A.J.; Salemink, H.W.M.; Wolter, J.H.; Blom, P.W.M.

    2003-01-01

    Scanning-tunneling spectroscopy experiments have been performed on conjugated polymer films and have been compared to a three-dimensional numerical model for charge injection and transport. It is found that field enhancement near the tip apex leads to significant changes in the injected current,

  3. Direct measurement of the microscale conductivity of conjugated polymer monolayers

    DEFF Research Database (Denmark)

    Bøggild, Peter; Grey, Francois; Hassenkam, T.

    2000-01-01

    The in-plane conductivity of conjugated polymer monolayers is mapped here for the first time on the microscale using a novel scanning micro four-point probe (see Figure). The probe allows the source, drain, and voltage electrodes to be positioned within the same domain and the mapping results...

  4. Rapid, facile synthesis of conjugated polymer zwitterions in ionic liquids

    Energy Technology Data Exchange (ETDEWEB)

    Page, Zachariah A. [Polymer Science & Engineering Department; Conte Center for Polymer Research; University of Massachusetts; Amherst, USA; Liu, Feng [Polymer Science & Engineering Department; Conte Center for Polymer Research; University of Massachusetts; Amherst, USA; Russell, Thomas P. [Polymer Science & Engineering Department; Conte Center for Polymer Research; University of Massachusetts; Amherst, USA; Emrick, Todd [Polymer Science & Engineering Department; Conte Center for Polymer Research; University of Massachusetts; Amherst, USA

    2014-01-01

    Ionic liquids (ILs) were utilized for the rapid air-stable Suzuki polymerization of polar zwitterionic thiophene monomers, precluding the need for volatile organic solvents, phosphine ligands and phase transfer catalysts typically used in conjugated polymer synthesis.

  5. Semiconductor-nanocrystal/conjugated polymer thin films

    Science.gov (United States)

    Alivisatos, A. Paul; Dittmer, Janke J.; Huynh, Wendy U.; Milliron, Delia

    2014-06-17

    The invention described herein provides for thin films and methods of making comprising inorganic semiconductor-nanocrystals dispersed in semiconducting-polymers in high loading amounts. The invention also describes photovoltaic devices incorporating the thin films.

  6. Polythiophenes containing in-chain cobaltabisdicarbollide centers.

    Science.gov (United States)

    Fabre, Bruno; Hao, Erhong; Lejeune, Zorabel M; Amuhaya, Edith K; Barrière, Frédéric; Garno, Jayne C; Vicente, M Graça H

    2010-03-01

    New cobalt(III) bis(dicarbollide) complexes covalently linked to two 2-oligothienyl units have been synthesized and electropolymerized in acetonitrile electrolyte in order to produce the corresponding polythiophene films containing in-chain metallic centers. The polymer films electrogenerated from the bithienyl (4b) and terthienyl (4c) derivatives display redox processes attributed to the Co(III)/Co(II) couple at ca. -1.1 V vs SCE and to the p-doping/undoping of the expected quaterthienyl and sexithienyl segments at ca. 0.8 V vs SCE. In contrast, the anodic oxidation of the thienyl (4a) derivative leads to passivation of the electrode surface. As the length of the oligothiophene substituents increases, the metallic and dicarbollide cage carbon atoms contributions in the HOMO decrease dramatically so that the highest occupied frontier orbitals of 4b and 4c can be considered as almost purely oligothiophene-based. From further UV-vis spectroscopy analysis, it is demonstrated that the polymer incorporating the sexithienyl segments is more conjugated than that with the quaterthienyl segments as the absorption maximum for the interband pi-pi* transition was observed at 410 and 448 nm for poly(4b) and poly(4c) respectively. Furthermore, these polymers display a more extended degree of conjugation than the parent oligothiophenes. Such features indicate a significant electronic delocalization through the cobaltabisdicarbollide moiety. Their conducting probe atomic force microscopy characterization indicates that poly(4b) and poly(4c) behave like heavily doped semiconductors rather than pure semiconductors. Mean conductivity values extracted from the current-voltage profiles are 1.4 x 10(-4) and 7.5 x 10(-4) S cm(-1) for poly(4b) and poly(4c), respectively. Such materials are found to be efficient for the electrocatalytic reduction of protons to dihydrogen, as exemplified for poly(4b). The overpotential for hydrogen evolution is significantly decreased by ca. 230 mV with

  7. Delocalization Drives Free Charge Generation in Conjugated Polymer Films

    Energy Technology Data Exchange (ETDEWEB)

    Rumbles, Garry [National Renewable Energy Laboratory (NREL), Golden, CO (United States); Reid, Obadiah G [National Renewable Energy Laboratory (NREL), Golden, CO (United States); Pace, Natalie A [National Renewable Energy Laboratory (NREL), Golden, CO (United States)

    2018-02-19

    We demonstrate that the product of photoinduced electron transfer between a conjugated polymer host and a dilute molecular sensitizer is controlled by the structural state of the polymer. Ordered semicrystalline solids exhibit free charge generation, while disordered polymers in the melt phase do not. We use photoluminescence (PL) and time-resolved microwave conductivity (TRMC) measurements to sweep through polymer melt transitions in situ. Free charge generation measured by TRMC turns off upon melting, whereas PL quenching of the molecular sensitizers remains constant, implying unchanged electron transfer efficiency. The key difference is the intermolecular order of the polymer host in the solid state compared to the melt. We propose that this order-disorder transition modulates the localization length of the initial charge-transfer state, which controls the probability of free charge formation.

  8. Hierarchical assembly of branched supramolecular polymers from (cyclic Peptide)-polymer conjugates.

    Science.gov (United States)

    Koh, Ming Liang; Jolliffe, Katrina A; Perrier, Sébastien

    2014-11-10

    We report the synthesis and assembly of (N-methylated cyclic peptide)-polymer conjugates for which the cyclic peptide is attached to either the α- or both α- and ω- end groups of a polymer. A combination of chromatographic, spectroscopic, and scattering techniques reveals that the assembly of the conjugates follows a two-level hierarchy, initially driven by H-bond formation between two N-methylated cyclic peptides, followed by unspecific, noncovalent aggregation of this peptide into small domains that behave as branching points and lead to the formation of branched supramolecular polymers.

  9. pi-Conjugated polymers for photovoltaics

    NARCIS (Netherlands)

    Zoombelt, A.P.

    2009-01-01

    Polymer solar cells employ a nanoscopic phase separation or bulk heterojunction (BHJ) between two complementary molecular based p and n-type organic semiconductors to convert sunlight directly into electricity. The operational principle involves a complex sequence of events, starting with the

  10. Controlling Film Morphology in Conjugated Polymer

    Science.gov (United States)

    Park, Lee Y.; Munro, Andrea M.; Ginger, David S.

    2009-01-01

    We study the effects of patterned surface chemistry on the microscale and nanoscale morphology of solution-processed donor/acceptor polymer-blend films. Focusing on combinations of interest in polymer solar cells, we demonstrate that patterned surface chemistry can be used to tailor the film morphology of blends of semiconducting polymers such as poly-[2-(3,7-dimethyloctyloxy)-5-methoxy-p-phenylenevinylene] (MDMO-PPV), poly-3-hexylthiophene (P3HT), poly[(9,9-dioctylflorenyl-2,7-diyl)-co-benzothiadiazole)] (F8BT), and poly(9,9-dioctylfluorene-co-bis-N,N’-(4-butylphenyl)-bis-N,N’-phenyl-1,4-phenylendiamine) (PFB) with the fullerene derivative, [6,6]-phenyl-C61-butyric acid methyl ester (PCBM). We present a method for generating patterned, fullerene-terminated monolayers on gold surfaces, and use microcontact printing and Dip-Pen Nanolithography (DPN) to pattern alkanethiols with both micro- and nanoscale features. After patterning with fullerenes and other functional groups, we backfill the rest of the surface with a variety of thiols to prepare substrates with periodic variations in surface chemistry. Spin coating polymer:PCBM films onto these substrates, followed by thermal annealing under nitrogen, leads to the formation of structured polymer films. We characterize these films with Atomic Force Microscopy (AFM), Raman spectroscopy, and fluorescence microscopy. The surface patterns are effective in guiding phase separation in all of the polymer:PCBM systems investigated, and lead to a rich variety of film morphologies that are inaccessible with unpatterned substrates. We demonstrate our ability to guide pattern formation in films thick enough of be of interest for actual device applications (up to 200 nm in thickness) using feature sizes as small as 100 nm. Finally, we show that the surface chemistry can lead to variations in film morphology on length scales significantly smaller than those used in generating the original surface patterns. The variety of

  11. Peptide/protein-polymer conjugates: synthetic strategies and design concepts.

    Science.gov (United States)

    Gauthier, Marc A; Klok, Harm-Anton

    2008-06-21

    This feature article provides a compilation of tools available for preparing well-defined peptide/protein-polymer conjugates, which are defined as hybrid constructs combining (i) a defined number of peptide/protein segments with uniform chain lengths and defined monomer sequences (primary structure) with (ii) a defined number of synthetic polymer chains. The first section describes methods for post-translational, or direct, introduction of chemoselective handles onto natural or synthetic peptides/proteins. Addressed topics include the residue- and/or site-specific modification of peptides/proteins at Arg, Asp, Cys, Gln, Glu, Gly, His, Lys, Met, Phe, Ser, Thr, Trp, Tyr and Val residues and methods for producing peptides/proteins containing non-canonical amino acids by peptide synthesis and protein engineering. In the second section, methods for introducing chemoselective groups onto the side-chain or chain-end of synthetic polymers produced by radical, anionic, cationic, metathesis and ring-opening polymerization are described. The final section discusses convergent and divergent strategies for covalently assembling polymers and peptides/proteins. An overview of the use of chemoselective reactions such as Heck, Sonogashira and Suzuki coupling, Diels-Alder cycloaddition, Click chemistry, Staudinger ligation, Michael's addition, reductive alkylation and oxime/hydrazone chemistry for the convergent synthesis of peptide/protein-polymer conjugates is given. Divergent approaches for preparing peptide/protein-polymer conjugates which are discussed include peptide synthesis from synthetic polymer supports, polymerization from peptide/protein macroinitiators or chain transfer agents and the polymerization of peptide side-chain monomers.

  12. Degradable conjugated polymers for the selective sorting of semiconducting carbon nanotubes

    Science.gov (United States)

    Gopalan, Padma; Arnold, Michael Scott; Kansiusarulsamy, Catherine Kanimozhi; Brady, Gerald Joseph; Shea, Matthew John

    2018-04-10

    Conjugated polymers composed of bi-pyridine units linked to 9,9-dialkyl fluorenyl-2,7-diyl units via imine linkages along the polymer backbone are provided. Also provided are semiconducting single-walled carbon nanotubes coated with the conjugated polymers and methods of sorting and separating s-SWCNTs from a sample comprising a mixture of s-SWCNTs and metallic single-walled carbon nanotubes using the conjugated polymers.

  13. Conformation sensitive charge transport in conjugated polymers

    International Nuclear Information System (INIS)

    Mattias Andersson, L.; Hedström, Svante; Persson, Petter

    2013-01-01

    Temperature dependent charge carrier mobility measurements using field effect transistors and density functional theory calculations are combined to show how the conformation dependent frontier orbital delocalization influences the hole- and electron mobilities in a donor-acceptor based polymer. A conformationally sensitive lowest unoccupied molecular orbital results in an electron mobility that decreases with increasing temperature above room temperature, while a conformationally stable highest occupied molecular orbital is consistent with a conventional hole mobility behavior and also proposed to be one of the reasons for why the material works well as a hole transporter in amorphous bulk heterojunction solar cells

  14. Quantum dot-polymer conjugates for stable luminescent displays.

    Science.gov (United States)

    Ghimire, Sushant; Sivadas, Anjaly; Yuyama, Ken-Ichi; Takano, Yuta; Francis, Raju; Biju, Vasudevanpillai

    2018-05-23

    The broad absorption of light in the UV-Vis-NIR region and the size-based tunable photoluminescence color of semiconductor quantum dots make these tiny crystals one of the most attractive antennae in solar cells and phosphors in electrooptical devices. One of the primary requirements for such real-world applications of quantum dots is their stable and uniform distribution in optically transparent matrices. In this work, we prepare transparent thin films of polymer-quantum dot conjugates, where CdSe/ZnS quantum dots are uniformly distributed at high densities in a chitosan-polystyrene copolymer (CS-g-PS) matrix. Here, quantum dots in an aqueous solution are conjugated to the copolymer by a phase transfer reaction. With the stable conjugation of quantum dots to the copolymer, we prevent undesired phase separation between the two and aggregation of quantum dots. Furthermore, the conjugate allows us to prepare transparent thin films in which quantum dots are uniformly distributed at high densities. The CS-g-PS copolymer helps us in not only preserving the photoluminescence properties of quantum dots in the film but also rendering excellent photostability to quantum dots at the ensemble and single particle levels, making the conjugate a promising material for photoluminescence-based devices.

  15. Photochemical stability of π-conjugated polymers for polymer solar cells: a rule of thumb

    DEFF Research Database (Denmark)

    Manceau, Matthieu; Bundgaard, Eva; Carlé, Jon Eggert

    2011-01-01

    A comparative photochemical stability study of a wide range of π-conjugated polymers relevant to polymer solar cells is presented. The behavior of each material has been investigated under simulated sunlight (1 sun, 1000 W m−2, AM 1.5G) and ambient atmosphere. Degradation was monitored during age...... ageing combining UV-visible and infrared spectroscopies. From the comparison of the collected data, the influence of the polymer chemical structure on its stability has been discussed. General rules relative to the polymer structure–stability relationship are proposed....

  16. Substituted Polyacetylenes Prepared with Rh Catalysts: From Linear to Network-Type Conjugated Polymers

    Czech Academy of Sciences Publication Activity Database

    Sedláček, J.; Balcar, Hynek

    2017-01-01

    Roč. 57, č. 1 (2017), s. 31-51 ISSN 1558-3724 Institutional support: RVO:61388955 Keywords : conjugated polymers * polyacetylenes * conjugated polymer networks Subject RIV: CF - Physical ; Theoretical Chemistry OBOR OECD: Polymer science Impact factor: 6.459, year: 2016

  17. Syntheses and optical properties of triphenylene-containing conjugated polymers

    International Nuclear Information System (INIS)

    Chou, C.-E.; Wang Degang; Bagui, Mahuya; Hsu, Jeffrey; Chakraborty, Sanjiban; Peng Zhonghua

    2010-01-01

    In this paper, we report the detailed synthesis and optical properties of three new conjugated polymers containing triphenylene units in the backbone. Polymer PTPT exhibits strong folding propensity and forms foldamers in both polar and nonpolar solvents. PTPA, with two long alkyl chains attached to the bridging phenyl ring, exhibits mainly as interchain aggregates in 'poor' solvents (DMSO and acetonitrile), but adopts a folding conformation in solvent mixtures with a high poor solvent content. PTPV, on the other hand, adopts a random nonfolding conformation in both polar and nonpolar solvents. The low folding propensity of PTPV is likely due to the added geometrical flexibility of the vinyl bonds. Among the three polymers, PTPV is most fluorescent with a fluorescence quantum yield as high as 0.87, suggesting its potential applications as light-emitting materials or fluorescence-based sensors. PTPT, on the other hand, with its strong folding property, may find applications as efficient charge-transporting materials.

  18. Indaceno-Based Conjugated Polymers for Polymer Solar Cells.

    Science.gov (United States)

    Yin, Yuli; Zhang, Yong; Zhao, Liancheng

    2018-01-04

    Polymer solar cells have received considerable attention due to the advantages of low material cost, tunable band gaps, ultralight weight, and high flexible properties, and they have been a promising organic photovoltaic technology for alternative non-renewable fossil fuels for the past decade. Inspired by these merits, numerous state-of-the-art organic photovoltaic materials have been constructed. Among them, indaceno-based polymer materials have made an impact in obtaining an impressive power conversion efficiency of more than 11%, which shows the momentous potential of this class of materials for commercial applications. In this review, recent progress of indaceno-based organic polymer solar cells are reviewed, and the structure-property device performance correlations of the reported materials are highlighted. Then, common regularities of these successful cases are collected, and encouraging viewpoints on the further development of more exciting indaceno-based organic photovoltaic materials are provided. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. Sensitive thermal transitions of nanoscale polymer samples using the bimetallic effect: application to ultra-thin polythiophene.

    Science.gov (United States)

    Ahumada, O; Pérez-Madrigal, M M; Ramirez, J; Curcó, D; Esteves, C; Salvador-Matar, A; Luongo, G; Armelin, E; Puiggalí, J; Alemán, C

    2013-05-01

    A sensitive nanocalorimetric technology based on microcantilever sensors is presented. The technology, which combines very short response times with very small sample consumption, uses the bimetallic effect to detect thermal transitions. Specifically, abrupt variations in the Young's modulus and the thermal expansion coefficient produced by temperature changes have been employed to detect thermodynamic transitions. The technology has been used to determine the glass transition of poly(3-thiophene methyl acetate), a soluble semiconducting polymer with different nanotechnological applications. The glass transition temperature determined using microcantilevers coated with ultra-thin films of mass = 10(-13) g is 5.2 °C higher than that obtained using a conventional differential scanning calorimeter for bulk powder samples of mass = 5 × 10(-3) g. Atomistic molecular dynamics simulations on models that represent the bulk powder and the ultra-thin films have been carried out to provide understanding and rationalization of this feature. Simulations indicate that the film-air interface plays a crucial role in films with very small thickness, affecting both the organization of the molecular chains and the response of the molecules against the temperature.

  20. Thiolated polymers: synthesis and in vitro evaluation of polymer-cysteamine conjugates.

    Science.gov (United States)

    Bernkop-Schnürch, A; Clausen, A E; Hnatyszyn, M

    2001-09-11

    The purpose of the present study was to synthesize and characterize novel thiolated polymers. Mediated by a carbodiimide cysteamine was covalently linked to sodium carboxymethylcellulose (CMC) and polycarbophil (PCP). The resulting CMC-cysteamine conjugates displayed 77.9+/-6.7 and 365.1+/-8.7 micromol thiol groups per gram of polymer, whereas the PCP-cysteamine conjugates showed 26.3+/-1.9 and 122.7+/-3.8 micromol thiol groups per gram of polymer (mean+/-S.D.; n=3). In aqueous solutions above pH 5.0 both modified polymers were capable of forming inter- and/or intra-molecular disulfide bonds. The reaction velocity of this oxidation process was accelerated with a decrease in the proton concentration. The oxidation proceeded more rapidly within thiolated CMC than within thiolated PCP. Permeation studies carried out in Ussing-type chambers with freshly excised intestinal mucosa from guinea pigs utilizing sodium fluorescein as model drug for the paracellular uptake revealed an enhancement ratio (R=P(app) (conjugate)/P(app) (control)) of 1.15 and 1.41 (mean+/-S.D.; n=3) for the higher thiolated CMC-cysteamine (0.5%; m/v) and PCP-cysteamine conjugate (1.0%; m/v), respectively. The decrease in the transepithelial electrical resistance values was in good correlation with the enhancement ratios. Due to a high crosslinking tendency by the formation of disulfide bonds stabilizing drug carrier systems based on thiolated polymers and a permeation enhancing effect, CMC- and PCP-cysteamine conjugates represent promising excipients for the development of novel drug delivery systems.

  1. Singlet Exciton Lifetimes in Conjugated Polymer Films for Organic Solar Cells

    KAUST Repository

    Dimitrov, Stoichko; Schroeder, Bob; Nielsen, Christian; Bronstein, Hugo; Fei, Zhuping; McCulloch, Iain; Heeney, Martin; Durrant, James

    2016-01-01

    The lifetime of singlet excitons in conjugated polymer films is a key factor taken into account during organic solar cell device optimization. It determines the singlet exciton diffusion lengths in polymer films and has a direct impact

  2. Controlling photophysical properties of ultrasmall conjugated polymer nanoparticles through polymer chain packing

    KAUST Repository

    Piwonski, Hubert Marek

    2017-05-16

    Applications of conjugated polymer nanoparticles (Pdots) for imaging and sensing depend on their size, fluorescence brightness and intraparticle energy transfer. The molecular design of conjugated polymers (CPs) has been the main focus of the development of Pdots. Here we demonstrate that proper control of the physical interactions between the chains is as critical as the molecular design. The unique design of twisted CPs and fine-tuning of the reprecipitation conditions allow us to fabricate ultrasmall (3.0–4.5 nm) Pdots with excellent photostability. Extensive photophysical and structural characterization reveals the essential role played by the packing of the polymer chains in the particles in the intraparticle spatial alignment of the emitting sites, which regulate the fluorescence brightness and the intraparticle energy migration efficiency. Our findings enhance understanding of the relationship between chain interactions and the photophysical properties of CP nanomaterials, providing a framework for designing and fabricating functional Pdots for imaging applications.

  3. Alcohol vapor sensory properties of nanostructured conjugated polymers

    International Nuclear Information System (INIS)

    Bearzotti, Andrea; Macagnano, Antonella; Pantalei, Simone; Zampetti, Emiliano; Venditti, Iole; Fratoddi, Ilaria; Vittoria Russo, Maria

    2008-01-01

    The response to relative humidity (RH) and alcohol vapors of resistive-type sensors based on nanobeads of conjugated polymers, namely polyphenylacetylene (PPA) and copolymer poly[phenylacetylene-(co-2-hydroxyethyl methacrylate)] (P(PA/HEMA)), were investigated. Sensors based on ordered arrays of these nanostructured polymeric materials showed stable and reproducible current intensity variations in the range 10-90% of relative humidity at room temperature. Both polymers also showed sensitivity to aliphatic chain primary alcohols, and a fine tuning of the sensor response was obtained by varying the chain length of the alcohol in relation to the polarity. The nanostructured feature of polymeric-based membranes seems to have an effect on the sensing response and an enhancement of the sensitivity was observed for the response to water and alcohol vapor variations with respect to previous studies based on amorphous polyphenylacetylene. High stability of the polymeric nanostructured membranes was detected with no aging after two weeks in continuum stressing measurement conditions.

  4. Thermo-cleavable solvents for printing conjugated polymers: Application in polymer solar cells

    DEFF Research Database (Denmark)

    Jørgensen, Mikkel; Hagemann, Ole; Alstrup, Jan

    2009-01-01

    large-scale production of polymer solar cells using screen printing. Screen-printed solar cells are still very inferior to state of the art P3HT/PCBM technology, but it is our view that it is necessary to explore these printing technologies if polymer solar cells are to ever become commercial products.......The synthesis and characterization of a number of so-called thermo-cleavable solvents are described with their application in all-air, all-solution and all-screen-printed polymer solar cells. These solvents were developed to meet some requirements for printing techniques such as long “open time...... (TGA) and high-temperature NMR established the onset temperature of decomposition, the rate of the reaction and the nature of the products. Printing experiments with inks based on these solvents together with conjugated polymers are exemplified for polymer solar cell devices to show how they enable...

  5. Carrier heating in disordered conjugated polymers in electric field

    Energy Technology Data Exchange (ETDEWEB)

    Vukmirovic, Nenad; Wang, Lin-Wang

    2010-01-26

    The electric field dependence of charge carrier transport and the effect of carrier heating in disordered conjugated polymers were investigated. A parameter-free multiscale methodology consisting of classical molecular dynamics simulation for the generation of the atomic structure, large system electronic structure and electron-phonon coupling constants calculations and the procedure for extracting the bulk polymer mobility, was used. The results suggested that the mobility of a fully disordered poly(3-hexylthiophene) (P3HT) polymer increases with electric field which is consistent with the experimental results on samples of regiorandom P3HT and different from the results on more ordered regioregular P3HT polymers, where the opposite trend is often observed at low electric fields. We calculated the electric field dependence of the effective carrier temperature and showed however that the effective temperature cannot be used to replace the joint effect of temperature and electric field, in contrast to previous theoretical results from phenomenological models. Such a difference was traced to originate from the use of simplified Miller-Abrahams hopping rates in phenomenological models in contrast to our considerations that explicitly take into account the electronic state wave functions and the interaction with all phonon modes.

  6. Effect of disorder on exciton dissociation in conjugated polymers

    International Nuclear Information System (INIS)

    Feng Yuwen; Zhao Hui; Chen Yuguang; Yan Yonghong

    2017-01-01

    By using a multi-configurational time-dependent Hartree–Fock (MCTDHF) method for the time-dependent Schrödinger equation and a Newtonian equation of motion for lattice, we investigate the disorder effects on the dissociation process of excitons in conjugated polymer chains. The simulations are performed within the framework of an extended version of the Su–Schrieffer–Heeger model modified to include on-site disorder, off-diagonal, electron–electron interaction, and an external electric field. Our results show that Coulomb correlation effects play an important role in determining the exciton dissociation process. The electric field required to dissociate an exciton can practically impossibly occur in a pure polymer chain, especially in the case of triplet exciton. However, when the on-site disorder effects are taken into account, this leads to a reduction in mean dissociation electric fields. As the disorder strength increases, the dissociation field decreases effectively. On the contrary, the effects of off-diagonal disorder are negative in most cases. Moreover, the dependence of exciton dissociation on the conjugated length is also discussed. (paper)

  7. Effects of the Substituents of Boron Atoms on Conjugated Polymers Containing B←N Units.

    Science.gov (United States)

    Liu, Jun; Wang, Tao; Dou, Chuandong; Wang, Lixiang

    2018-06-15

    Organoboron chemistry is a new tool to tune the electronic structures and properties of conjugated polymers, which are important for applications in organic opto-electronic devices. To investigate the effects of substituents of boron atoms on conjugated polymers, we synthesized three conjugated polymers based on double B←N bridged bipyridine (BNBP) with various substituents on the boron atoms. By changing the substituents from four phenyl groups and two phenyl groups/two fluorine atoms to four fluorine atoms, the BNBP-based polymers show the blue-shifted absorption spectra, decreased LUMO/HOMO energy levels and enhanced electron affinities, as well as the increased electron mobilities. Moreover, these BNBP-based polymers can be used as electron acceptors for all-polymer solar cells. These results demonstrate that the substituents of boron atoms can effectively modulate the electronic properties and applications of conjugated polymers. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. Theoretical and computational studies of excitons in conjugated polymers

    Science.gov (United States)

    Barford, William; Bursill, Robert J.; Smith, Richard W.

    2002-09-01

    We present a theoretical and computational analysis of excitons in conjugated polymers. We use a tight-binding model of π-conjugated electrons, with 1/r interactions for large r. In both the weak-coupling limit (defined by W>>U) and the strong-coupling limit (defined by Wparticle models. We compare these to density matrix renormalization group (DMRG) calculations, and find good agreement in the extreme limits. We use these analytical results to interpret the DMRG calculations in the intermediate-coupling regime (defined by W~U), most applicable to conjugated polymers. We make the following conclusions. (1) In the weak-coupling limit the bound states are Mott-Wannier excitons, i.e., conduction-band electrons bound to valence-band holes. Singlet and triplet excitons whose relative wave functions are odd under a reflection of the relative coordinate are degenerate. Thus, the 2 1A+g and 1 3A-g states are degenerate in this limit. (2) In the strong-coupling limit the bound states are Mott-Hubbard excitons, i.e., particles in the upper Hubbard band bound to holes in the lower Hubbard band. These bound states occur in doublets of even and odd parity excitons. Triplet excitons are magnons bound to the singlet excitons, and hence are degenerate with their singlet counterparts. (3) In the intermediate-coupling regime Mott-Wannier excitons are the more appropriate description for large dimerization, while for the undimerized chain Mott-Hubbard excitons are the correct description. For dimerizations relevant to polyacetylene and polydiacetylene both Mott-Hubbard and Mott-Wannier excitons are present. (4) For all coupling strengths an infinite number of bound states exist for 1/r interactions for an infinite polymer. As a result of the discreteness of the lattice and the restrictions on the exciton wave functions in one dimension, the progression of states does not follow the Rydberg series. In practice, excitons whose particle-hole separation exceeds the length of the polymer

  9. Thin Films Formed from Conjugated Polymers with Ionic, Water-Soluble Backbones

    NARCIS (Netherlands)

    Voortman, Thomas P; Chiechi, Ryan C

    2015-01-01

    This paper compares the morphologies of films of conjugated polymers in which the backbone (main chain) and pendant groups are varied between ionic/hydrophilic and aliphatic/hydrophobic. We observe that conjugated polymers in which the pendant groups and backbone are matched, either ionic-ionic or

  10. Bio-degradable highly fluorescent conjugated polymer nanoparticles for bio-medical imaging applications.

    Science.gov (United States)

    Repenko, Tatjana; Rix, Anne; Ludwanowski, Simon; Go, Dennis; Kiessling, Fabian; Lederle, Wiltrud; Kuehne, Alexander J C

    2017-09-07

    Conjugated polymer nanoparticles exhibit strong fluorescence and have been applied for biological fluorescence imaging in cell culture and in small animals. However, conjugated polymer particles are hydrophobic and often chemically inert materials with diameters ranging from below 50 nm to several microns. As such, conjugated polymer nanoparticles cannot be excreted through the renal system. This drawback has prevented their application for clinical bio-medical imaging. Here, we present fully conjugated polymer nanoparticles based on imidazole units. These nanoparticles can be bio-degraded by activated macrophages. Reactive oxygen species induce scission of the conjugated polymer backbone at the imidazole unit, leading to complete decomposition of the particles into soluble low molecular weight fragments. Furthermore, the nanoparticles can be surface functionalized for directed targeting. The approach opens a wide range of opportunities for conjugated polymer particles in the fields of medical imaging, drug-delivery, and theranostics.Conjugated polymer nanoparticles have been applied for biological fluorescence imaging in cell culture and in small animals, but cannot readily be excreted through the renal system. Here the authors show fully conjugated polymer nanoparticles based on imidazole units that can be bio-degraded by activated macrophages.

  11. Understanding Interfacial Alignment in Solution Coated Conjugated Polymer Thin Films

    International Nuclear Information System (INIS)

    Qu, Ge; Zhao, Xikang; Newbloom, Gregory M.; Zhang, Fengjiao; Mohammadi, Erfan

    2017-01-01

    Domain alignment in conjugated polymer thin films can significantly enhance charge carrier mobility. However, the alignment mechanism during meniscus-guided solution coating remains unclear. Furthermore, interfacial alignment has been rarely studied despite its direct relevance and critical importance to charge transport. In this study, we uncover a significantly higher degree of alignment at the top interface of solution coated thin films, using a donor–acceptor conjugated polymer, poly(diketopyrrolopyrrole-co-thiopheneco- thieno[3,2-b]thiophene-co-thiophene) (DPP2T-TT), as the model system. At the molecular level, we observe in-plane π–π stacking anisotropy of up to 4.8 near the top interface with the polymer backbone aligned parallel to the coating direction. The bulk of the film is only weakly aligned with the backbone oriented transverse to coating. At the mesoscale, we observe a well-defined fibril-like morphology at the top interface with the fibril long axis pointing toward the coating direction. Significantly smaller fibrils with poor orientational order are found on the bottom interface, weakly aligned orthogonal to the fibrils on the top interface. The high degree of alignment at the top interface leads to a charge transport anisotropy of up to 5.4 compared to an anisotropy close to 1 on the bottom interface. We attribute the formation of distinct interfacial morphology to the skin-layer formation associated with high Peclet number, which promotes crystallization on the top interface while suppressing it in the bulk. As a result, we further infer that the interfacial fibril alignment is driven by the extensional flow on the top interface arisen from increasing solvent evaporation rate closer to the meniscus front.

  12. Particle-in-a-box model of exciton absorption and electroabsorption in conjugated polymers

    Science.gov (United States)

    Pedersen, Thomas G.

    2000-12-01

    The recently proposed particle-in-a-box model of one-dimensional excitons in conjugated polymers is applied in calculations of optical absorption and electroabsorption spectra. It is demonstrated that for polymers of long conjugation length a superposition of single exciton resonances produces a line shape characterized by a square-root singularity in agreement with experimental spectra near the absorption edge. The effects of finite conjugation length on both absorption and electroabsorption spectra are analyzed.

  13. Preparation and characterization of conjugated polymers made by postpolymerization reactions of alternating polyketones.

    Science.gov (United States)

    Cheng, Chen; Guironnet, Damien; Barborak, James; Brookhart, Maurice

    2011-06-29

    Conjugated polymers possessing a poly(2,5-dimethylene-2,5-dihydrofuran) backbone were prepared through postpolymerization reaction of styrenic polyketones with bromine in one-pot reactions. The modification is proposed to proceed via condensation of two repeating units to form a fully characterized polymer with a poly(2,5-dimethylenetetrahydrofuran) backbone. Subsequent bromination and elimination of HBr yield a polymer with a fully conjugated carbon backbone. The new conjugated polymers were characterized by NMR, IR, and UV-vis spectroscopies and by CV. These polymers have strong absorption in the visible region, with the absorption peaks shifted to the NIR region upon doping with acids. The ease of the synthesis of the starting polyketone and of the modifications allows large-scale preparation of those conjugated polymers.

  14. Use of Polythiophene as a Temperature Sensor

    Directory of Open Access Journals (Sweden)

    D. S. KELKAR

    2011-06-01

    Full Text Available The polythiophene was chemically synthesized using 2,5–dibromothiophene by debromination with magnesium, catalyzed by nickel chloride. The synthesized polymer was undoped using liquid ammonia and then doped again using 5 % aqueous FeCl3 for 2.5 and 5 hour duration. Characterization of undoped as well as doped samples using elemental analysis has been carried out. Elemental analysis shows that concentration of Fe+ ions increases as the duration of doping increases. All samples were pressed into pellets of about 1cm in diameter and were coated, on both sides, by aluminum using vacuum deposition technique. I – V measurements of undoped and FeCl3 doped samples, after coating have been carried out using two probe method. I – V measurements were carried out by applying +ve potential on one side from 0 V to 1 V in steps of 0.1 V and then from 1 V to 10 V in steps of 1 V. The measurements were again carried out after interchanging the polarity of the applied voltage. I – V measurements were also carried out at room temperature as well as at various temperatures in the range from 301 K to 331 K in steps of 5K. These characteristics are just similar to the characteristics of conventional p – n junction diode. The effect of doping is to reduce the knee voltage. I – V characteristics of undoped polythiophene after interchanging the polarity (like reverse bias condition in p–n junction diode at various temperature are plotted. From the graphs it is observed that the magnitude of current increases as temperature is increased. A straight line graph of temperature versus current for an applied voltage of 3 V indicates that undoped polythiophene can be used as temperature sensor in the temperature range from 301 K to 331 K.

  15. Charge transport in conjugated polymers: a multiscale picture

    Science.gov (United States)

    Ruehle, Victor; Kirkpatrick, James; Kremer, Kurt; Andrienko, Denis

    2009-03-01

    A framework to study charge transport in conjugated polymers using realistic morphologies is developed. First, the atomistic force field is refined using first-principles calculations. Systematic coarse graining is then performed to extend simulation times and system sizes accessible to molecular dynamics simulations. Material morphologies are generated using the coarse grained and atomistic models. Finally, the charge mobility is obtained using temperature activated hopping picture for charge transport [1]. The framework is tested on neutral and oxidized polypyrrole with different structural ordering [2]. [4pt] [1] J. Kirkpatrick, V. Marcon, J. Nelson, K. Kremer, D. Andrienko, Phys. Rev. Lett. 98, 227402 (2007)[0pt] [2] V. Ruehle, J. Kirkpatrick, K. Kremer, D. Andrienko, Phys. Stat. Solidi B, 245, 844 (2008)

  16. Hopping approach towards exciton dissociation in conjugated polymers

    International Nuclear Information System (INIS)

    Emelianova, E. V.; Auweraer, M. van der; Baessler, H.

    2008-01-01

    By employing random walk an analytic theory for the dissociation of singlet excitons in a random organic solid, for instance, a conjugated polymer, has been developed. At variance of conventional three-dimensional Onsager theory, it is assumed that an exciton with finite lifetime can first transfer endothermically an electron to an adjacent site, thereby generating a charge transfer state whose energy is above the energy of that of the initial exciton. In a second step the latter can fully dissociate in accordance with Onsager's concept Brownian motion. The results indicate that, depending of the energy required for the first jump, the first jump contributes significantly to the field dependence of the dissociation yield. Disorder weakens the temperature dependence of the yield dramatically and precludes extracting information on the exciton binding energy from it

  17. Control of gain in conjugated polymers and perylene dyes

    International Nuclear Information System (INIS)

    Sheridan, A.

    2001-03-01

    This thesis presents an investigation into the factors which control the gain and amplification properties in conjugated materials. Conjugated polymers and perylene dyes are highly fluorescent, are easy to process into thin films, and exhibit strong amplification over a broad gain bandwidth making them ideal for use in lasers and amplifiers. The stimulated emission created when thin films of the red emitting polymer poly(2-methoxy-5-(2'-ethylhexyloxy)-p-phenylenvinylene) (MEH-PPV) were photoexcited with high energy laser pulses was investigated. This was characterised by a dramatic narrowing of the emission spectrum which has been assigned to amplified spontaneous emission (ASE). The emission was found to have a gaussian profile and the gain coefficient was found to be 4 cm -1 . The temperature dependence of the absorption, photoluminescence and ASE of films of MEH-PPV was measured. The effect of film morphology on the photophysical properties was investigated by using films cast from two spinning solvents, chlorobenzene (CB) and tetrahydrofuran (THF). Film morphology was found to greatly affect the temperature dependence. A particularly important property is the spectral position of the ASE and the factors which affect it. By controlling the film thickness close to the cut-off thickness for waveguiding in the polymer film it was shown that the peak position of the ASE could be tuned by 31 nm. Modelling of the waveguide modes in the polymer films was used to explain this effect. The cut-off wavelength for each film was measured and good agreement with the theory was found. In order to investigate ways in which energy transfer could be used to control the emission, two perylene dyes were used as a donor-acceptor pair in a host matrix of poly methymethacralate (PMMA). The position of the ASE was found to depend on the acceptor concentration. Measurements of the photoluminescence quantum yield and time-resolved luminescence measurements showed that the energy transfer

  18. Theory of optical transitions in conjugated polymers. I. Ideal systems.

    Science.gov (United States)

    Barford, William; Marcus, Max

    2014-10-28

    We describe a theory of linear optical transitions in conjugated polymers. The theory is based on three assumptions. The first is that the low-lying excited states of conjugated polymers are Frenkel excitons coupled to local normal modes, described by the Frenkel-Holstein model. Second, we assume that the relevant parameter regime is ℏω ≪ J, i.e., the adiabatic regime, and thus the Born-Oppenheimer factorization of the electronic and nuclear degrees of freedom is generally applicable. Finally, we assume that the Condon approximation is valid, i.e., the exciton-polaron wavefunction is essentially independent of the normal modes. Using these assumptions we derive an expression for an effective Huang-Rhys parameter for a chain (or chromophore) of N monomers, given by S(N) = S(1)/IPR, where S(1) is the Huang-Rhys parameter for an isolated monomer. IPR is the inverse participation ratio, defined by IPR = (∑(n)|Ψ(n)|(4))(-1), where Ψ(n) is the exciton center-of-mass wavefunction. Since the IPR is proportional to the spread of the exciton center-of-mass wavefunction, this is a key result, as it shows that S(N) decreases with chain length. As in molecules, in a polymer S(N) has two interpretations. First, ℏωS(N) is the relaxation energy of an excited state caused by its coupling to the normal modes. Second, S(N) appears in the definition of an effective Franck-Condon factor, F(0v)(N) = S(N)(v)exp ( - S(N))/v! for the vth vibronic manifold. We show that the 0 - 0 and 0 - 1 optical intensities are proportional to F00(N) and F01(N), respectively, and thus the ratio of the 0 - 1 to 0 - 0 absorption and emission intensities are proportional to S(N). These analytical results are checked by extensive DMRG calculations and found to be generally valid, particularly for emission. However, for large chain lengths higher-lying quasimomentum exciton states become degenerate with the lowest vibrational excitation of the lowest exciton state. When this happens there is

  19. Multifunctional adhesive polymers: Preactivated thiolated chitosan-EDTA conjugates.

    Science.gov (United States)

    Netsomboon, Kesinee; Suchaoin, Wongsakorn; Laffleur, Flavia; Prüfert, Felix; Bernkop-Schnürch, Andreas

    2017-02-01

    The aim of this study was to synthesis preactivated thiolated chitosan-EDTA (Ch-EDTA-cys-2MNA) conjugates exhibiting in particular high mucoadhesive, cohesive and chelating properties. Thiol groups were coupled with chitosan by carbodiimide reaction and further preactivated by attachment with 2-mercaptonicotinic acid (2MNA) via disulfide bond formation. Determinations of primary amino and sulfhydryl groups were performed by TNBS and Ellman's tests, respectively. Cytotoxicity was screened by resazurin assay in Caco-2 cells. Mucoadhesive properties and bivalent cation binding capacity with Mg 2+ and Ca 2+ in comparison to chitosan-EDTA (Ch-EDTA) and thiolated Ch-EDTA (Ch-EDTA-cys) were evaluated. Determination of 2MNA and total sulfhydryl groups indicated that 80% of thiol groups were preactivated. The results from cytotoxicity studies demonstrated that Ch-EDTA-cys and Ch-EDTA-cys-2MNA were not toxic to the cells at the polymer test concentration of 0.25% (w/v) while cell viability decreased by increasing the concentration of Ch-EDTA. Although EDTA molecule was modified by thiolation and preactivation, approximately 50% of chelating properties of the conjugates were maintained compared to Ch-EDTA. Ch-EDTA-cys-2MNA adhered on freshly excised porcine intestinal mucosa up to 6h while Ch-EDTA adhered for just 1h. According to the combination of mucoadhesive and chelating properties of the conjugates synthesized in this study, Ch-EDTA-cys-2MNA might be useful for various mucosal drug delivery systems. Copyright © 2016 Elsevier B.V. All rights reserved.

  20. Impact of Backbone Fluorination on π-Conjugated Polymers in Organic Photovoltaic Devices: A Review

    Directory of Open Access Journals (Sweden)

    Nicolas Leclerc

    2016-01-01

    Full Text Available Solution-processed bulk heterojunction solar cells have experienced a remarkable acceleration in performances in the last two decades, reaching power conversion efficiencies above 10%. This impressive progress is the outcome of a simultaneous development of more advanced device architectures and of optimized semiconducting polymers. Several chemical approaches have been developed to fine-tune the optoelectronics and structural polymer parameters required to reach high efficiencies. Fluorination of the conjugated polymer backbone has appeared recently to be an especially promising approach for the development of efficient semiconducting polymers. As a matter of fact, most currently best-performing semiconducting polymers are using fluorine atoms in their conjugated backbone. In this review, we attempt to give an up-to-date overview of the latest results achieved on fluorinated polymers for solar cells and to highlight general polymer properties’ evolution trends related to the fluorination of their conjugated backbone.

  1. Control of charge carrier dynamics in disordered conjugated polymers

    Energy Technology Data Exchange (ETDEWEB)

    Hertel, Dirk [Physical Chemistry, University of Cologne, Luxemburgerstr. 116, 50939 Cologne, Germany, (Germany)

    2011-07-01

    We developed a new method to probe charge carrier mobility on ultrafast time scale. It is based on electric field induced second harmonic generation. The method is applied to prototypical amorphous conjugated polymers of the polyphenylene- and polyfluorene-type. Typically the carrier mobility in these organic polymers decreases with time in a power law fashion from about 1 cm{sup 2}Vs{sup -1} at 1 ps to its stationary value of about 10{sup -6} cm{sup 2}Vs{sup -1} in hundreds of ns. The dynamics of the mobility is discussed. It is shown, that in nanoscale devices the macroscopic mobility is not adequate to describe charge transport. We study the influence of disorder, morphology and temperature on ultrafast transport. At early times the transport is dominated by tunneling and disorder plays already an essential role. Comparison of transient photocurrents with Monte-Carlo simulation reveals that on-chain transport has to be invoked to rationalize our results. The hopping rates for intrachain transport are much larger compared with interchain transport. The results give access to essential transport properties for the development of advanced theoretical models and may help to design improved solar cells.

  2. Correlations between structure and optoelectronic properties of conjugated polymers

    International Nuclear Information System (INIS)

    Sims, Marc

    2002-01-01

    An understanding of the fundamental processes that govern the electro-optical properties of conjugated polymers is essential for the improvement of polymer light-emitting diodes (PLEDs). The majority of the work in this thesis comprises a study on a group of sterically congested poly(para-phenylenevinylene)s (PPVs). It deals initially with the discovery and development of a highly ordered crystalline phase of a chloro-derived n-butyl analogue. A thorough structural characterisation of this phase is then made from the results of X-ray Diffraction, FT-IR and Raman scattering spectroscopies. The effective conjugation length of the chains that comprise the crystalline sample is longer than that found in two relatively disordered films, one that was prepared by spin-coating and the other by drop-casting. The spin-coated film was found to exhibit a higher photoluminescence quantum efficiency (PLQE) value than the drop-cast film, which has been attributed to the presence of lower density of aggregate states in the former. The PLQE of the crystalline sample is considerably lower than that of both of the films and this is ascribed to the rapid migration of excitons to defect sites e.g. grain boundaries. PLE measurements for all the samples strongly suggest that singlet exciton quenching is intimately related to energy migration processes. Through the study of a novel, reversible, light-induced photoluminescence quenching effect, it was concluded that photogenerated polaronic species can be trapped sufficiently deeply that they can stabilise for periods in excess of hours at low temperatures. Furthermore, it is demonstrated that the photogenerated polaronic species are less stable in the crystalline sample, yet most stable in the most disordered spin-cast film. It is shown by excitation into the tail states of the crystalline sample that the first vibronic feature in the quasi-resonantly excited PL spectrum undergoes gain. This phenomenon is not observed in the more

  3. Hemoglobin Detection on a Microfluidic Sensor Chip with a Partially Conjugated Polymer

    International Nuclear Information System (INIS)

    Eo, Soo Han; Won, Kwang Jae; Song, Simon; Yoon, Bora; Kim, Jong Man

    2010-01-01

    The development of efficient chemosensors based on the conjugated polymers has been the central focus of a large number of recent research programs. The presence of extensively delocalized electrons and conformational restrictions of the backbone structures make conjugated polymers attractive sensory materials. In these polymers, molecular recognition events influence electronic absorption and emission properties. Thus, a wide variety of conjugated polymer-based sensors have been investigated. However, the majority of the conjugated polymer sensors described to date have been explored in the form of solutions or thin films. Most biologically interesting target molecules, such as proteins, carbohydrates, nucleic acids, or ions, are only soluble in water. Thus, it is desirable to use water-soluble conjugated polymers as sensor matrices. In general, in order to make water-soluble conjugated polymers tedious procedures are required since most synthetic methods developed for this purpose are incompatible with sidechain functionalities. Accordingly, protecting group strategies are required to prepare polymers with requisite functional groups that foster water solubility

  4. Molecular design toward highly efficient photovoltaic polymers based on two-dimensional conjugated benzodithiophene.

    Science.gov (United States)

    Ye, Long; Zhang, Shaoqing; Huo, Lijun; Zhang, Maojie; Hou, Jianhui

    2014-05-20

    As researchers continue to develop new organic materials for solar cells, benzo[1,2-b:4,5-b']dithiophene (BDT)-based polymers have come to the fore. To improve the photovoltaic properties of BDT-based polymers, researchers have developed and applied various strategies leading to the successful molecular design of highly efficient photovoltaic polymers. Novel polymer materials composed of two-dimensional conjugated BDT (2D-conjugated BDT) have boosted the power conversion efficiency of polymer solar cells (PSCs) to levels that exceed 9%. In this Account, we summarize recent progress related to the design and synthesis of 2D-conjugated BDT-based polymers and discuss their applications in highly efficient photovoltaic devices. We introduce the basic considerations for the construction of 2D-conjugated BDT-based polymers and systematic molecular design guidelines. For example, simply modifying an alkoxyl-substituted BDT to form an alkylthienyl-substituted BDT can improve the polymer hole mobilities substantially with little effect on their molecular energy level. Secondly, the addition of a variety of chemical moieties to the polymer can produce a 2D-conjugated BDT unit with more functions. For example, the introduction of a conjugated side chain with electron deficient groups (such as para-alkyl-phenyl, meta-alkoxyl-phenyl, and 2-alkyl-3-fluoro-thienyl) allowed us to modulate the molecular energy levels of 2D-conjugated BDT-based polymers. Through the rational design of BDT analogues such as dithienobenzodithiophene (DTBDT) or the insertion of larger π bridges, we can tune the backbone conformations of these polymers and modulate their photovoltaic properties. We also discuss the influence of 2D-conjugated BDT on polymer morphology and the blends of these polymers with phenyl-C61 (or C71)-butyric acid methyl ester (PCBM). Finally, we summarize the various applications of the 2D-conjugated BDT-based polymers in highly efficient PSC devices. Overall, this Account

  5. Two-dimensional charge transport in self-organized, high-mobility conjugated polymers

    DEFF Research Database (Denmark)

    Sirringhaus, H.; Brown, P.J.; Friend, R.H.

    1999-01-01

    Self-organization in many solution-processed, semiconducting conjugated polymers results in complex microstructures, in which ordered microcrystalline domains are embedded in an amorphous matrix(I). This has important consequences for electrical properties of these materials: charge transport...... of the ordered microcrystalline domains in the conjugated polymer poly(3-hexylthiophene), P3HT, Self-organization in P3HT results in a lamella structure with two-dimensional conjugated sheets formed by interchain stacking. We find that, depending on processing conditions, the lamellae can adopt two different...... of polymer transistors in logic circuits(5) and active-matrix displays(4,6)....

  6. Nanocomposites based on titanium dioxide and polythiophene: structure and properties

    Czech Academy of Sciences Publication Activity Database

    Vu, Q. T.; Pavlík, Martin; Hebestreit, N.; Rammelt, U.; Plieth, W.; Pfleger, Jiří

    2005-01-01

    Roč. 65, 1-2 (2005), s. 69-77 ISSN 1381-5148. [International Conference on Polymers and Organic Chemistry /11./. Prague, 18.06.2004-23.06.2004] R&D Projects: GA AV ČR IAA4050406 Grant - others:European Graduate School: Advanced Polymeric Materials(XE) IGK720 Institutional research plan: CEZ:AV0Z40500505 Keywords : polythiophene * titanium dioxide * nanocomposites Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 1.565, year: 2005

  7. Asymmetric diketopyrrolopyrrole conjugated polymers for field-effect transistors and polymer solar cells processed from a non-chlorinated solvent

    NARCIS (Netherlands)

    Ji, Y.; Xiao, C.; Wang, Q.; Zhang, J.; Li, C.; Wu, Y.; Wei, Z.; Zhan, X.; Hu, W.; Wang, Z.; Janssen, R.A.J.; Li, W.W.

    2016-01-01

    Newly designed asymmetric diketopyrrolopyrrole conjugated polymers with two different aromatic substituents possess a hole mobility of 12.5 cm2 V−1 s−1 in field-effect transistors and a power conversion efficiency of 6.5% in polymer solar cells, when solution processed from a nonchlorinated

  8. Carrier Transport Enhancement in Conjugated Polymers through Interfacial Self-Assembly of Solution-State Aggregates

    KAUST Repository

    Zhao, Kui; Khan, Hadayat Ullah; Li, Ruipeng; Hu, Hanlin; Amassian, Aram

    2016-01-01

    and extension of the conjugated backbone of the polymer which clearly translate to significant improvements of carrier transport at the semiconductor-dielectric interface in organic thin film transistors. This study points to opportunities in combining

  9. Synthesis and characterization of a low bandgap conjugated polymer for bulk heterojunction photovoltaic cells

    NARCIS (Netherlands)

    Dhanabalan, A.; Duren, van J.K.J.; Hal, van P.A.; Dongen, van J.L.J.; Janssen, R.A.J.

    2001-01-01

    Low optical bandgap conjugated polymers may improve the efficiency of organic photovoltaic devices by increasing the absorption in the visible and near infrared region of the solar spectrum. Here we demonstrate that condensation polymerization of

  10. Exploration of a Doxorubicin-Polymer Conjugate in Lipid-Polymer Hybrid Nanoparticle Drug Delivery

    Science.gov (United States)

    Lough, Emily

    Nanoparticle (NP) drug delivery is a major focus in the research community because of its potential to use existing drugs in safer and more effective ways. Chemotherapy encapsulation in NPs shields the drug from the rest of the body while it is within the NP, with less systemic exposure leading to fewer off-target effects of the drug. However, passive loading of drugs into NPs is a suboptimal method, often leading to burst release upon administration. This work explores the impact of incorporating the drug-polymer conjugate doxorubicin-poly (lactic-co-glycolic) acid (Dox-PLGA) into a lipid-polymer hybrid nanoparticle (LPN). The primary difference in using a drug-polymer conjugate for NP drug delivery is the drug's release kinetics. Dox-PLGA LPNs showed a more sustained and prolonged release profile over 28 days compared to LPNs with passively loaded, unconjugated doxorubicin. This sustained release translates to cytotoxicity; when systemic circulation was simulated using dialysis, Dox-PLGA LPNs retained their cytotoxicity at a higher level than the passively loaded LPNs. The in vivo implication of preserving cytotoxic potency through a slower release profile is that the majority of Dox delivered via Dox-PLGA LPNs will be kept within the LPN until it reaches the tumor. This will result in fewer systemic side effects and more effective treatments given the higher drug concentration at the tumor site. An intriguing clinical application of this drug delivery approach lies in using Dox-PLGA LPNs to cross the blood-brain barrier (BBB). The incorporation of Dox-PLGA is hypothesized to have a protective effect on the BBB as its slow release profile will prevent drug from harming the BBB. Using induced pluripotent stem cells differentiated to human brain microvascular endothelial cells that comprise the BBB, the Dox-PLGA LPNs were shown to be less destructive to the BBB than their passively loaded counterparts. Dox-PLGA LPNs showed superior cytotoxicity against plated tumor

  11. Simple Protein Modification Using Zwitterionic Polymer to Mitigate the Bioactivity Loss of Conjugated Insulin.

    Science.gov (United States)

    Xie, Jinbing; Lu, Yang; Wang, Wei; Zhu, Hui; Wang, Zhigang; Cao, Zhiqiang

    2017-06-01

    Polymer-protein conjugation has been extensively explored toward a better protein drug with improved pharmacokinetics. However, a major problem with polymer-protein conjugation is that the polymers drastically reduce the bioactivity of the modified protein. There is no perfect solution to prevent the bioactivity loss, no matter the polymer is conjugated in a non-site specific way, or a more complex site-specific procedure. Here the authors report for the first time that when zwitterionic carboxybetaine polymer (PCB) is conjugated to insulin through simple conventional coupling chemistry. The resulting PCB-insulin does not show a significant reduction of in vitro bioactivity. The obtained PCB-insulin shows two significant advantages as a novel pharmaceutical agent. First, its therapeutic performance is remarkable. For PCB-insulin, there is a 24% increase of in vivo pharmacological activity of lowering blood glucose compared with native insulin. Such uncommonly seen increase has rarely been reported and is expected to be due to both the improved pharmacokinetics and retained bioactivity of PCB-insulin. Second, the production is simple from manufacturing standpoints. Conjugation procedure involves only one-step coupling reaction without complex site-specific linkage technique. The synthesized PCB-insulin conjugates do not require chromatographic separation to purify and obtain particular isoforms. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. Conjugated Polymer with Intrinsic Alkyne Units for Synergistically Enhanced Raman Imaging in Living Cells.

    Science.gov (United States)

    Li, Shengliang; Chen, Tao; Wang, Yunxia; Liu, Libing; Lv, Fengting; Li, Zhiliang; Huang, Yanyi; Schanze, Kirk S; Wang, Shu

    2017-10-16

    Development of Raman-active materials with enhanced and distinctive Raman vibrations in the Raman-silent region (1800-2800 cm -1 ) is highly required for specific molecular imaging of living cells with high spatial resolution. Herein, water-soluble cationic conjugated polymers (CCPs), poly(phenylene ethynylene) (PPE) derivatives, are explored for use as alkyne-state-dependent Raman probes for living cell imaging due to synergetic enhancement effect of alkyne vibrations in Raman-silent region compared to alkyne-containing small molecules. The enhanced alkyne signals result from the integration of alkyne groups into the rigid backbone and the delocalized π-conjugated structure. PPE-based conjugated polymer nanoparticles (CPNs) were also prepared as Raman-responsive nanomaterials for distinct imaging application. This work opens a new way into the development of conjugated polymer materials for enhanced Raman imaging. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  13. Laterally Ordered Bulk Heterojunction of Conjugated Polymers : Nanoskiving a Jelly Roll

    NARCIS (Netherlands)

    Lipomi, Darren J.; Chiechi, Ryan C.; Reus, William F.; Whitesides, George M.

    2008-01-01

    This paper describes the fabrication of a nanostructured heterojunction of two conjugated polymers by a three-step process: i) spin-coating a multilayered film of the two polymers, ii) rolling the film into a cylinder (a ‘‘jelly roll’’) and iii) sectioning the film perpendicular to the axis of the

  14. Ethylene glycol oxidation on Pt and Pt-Ru nanoparticle decorated polythiophene/multiwalled carbon nanotube composites for fuel cell applications

    International Nuclear Information System (INIS)

    Selvaraj, Vaithilingam; Alagar, Muthukaruppan

    2008-01-01

    A novel supporting material containing polythiophene (PTh) and multiwalled carbon nanotubes (MWCNTs) (PTh-CNTs) is prepared by in situ polymerization of thiophene on carbon nanotubes using FeCl 3 as oxidizing agent under sonication. The prepared polythiophene/CNT composites are further decorated with Pt and Pt-Ru nanoparticles by chemical reduction of the corresponding metal salts using HCHO as reducing agent at pH = 11 (Pt/PTh-CNT and Pt-Ru/PTh-CNT). The fabricated composite films decorated with nanoparticles were investigated towards the electrochemical oxidation of ethylene glycol (EG). The presence of carbon nanotubes in conjugation with a conducting polymer produces a good catalytic effect, which might be due to the higher electrochemically accessible surface areas, electronic conductivity and easier charge-transfer at polymer/electrolyte interfaces, which allows higher dispersion of Pt and Pt-Ru nanoparticles. Such nanoparticle modified PTh-CNT electrodes exhibit better catalytic behavior towards ethylene glycol oxidation. Results show that Pt/PTh-CNT and Pt-Ru/PTh-CNT modified electrodes show enhanced electrocatalytic activity and stability towards the electro-oxidation of ethylene glycol than the Pt/PTh electrodes, which shows that the composite film is more promising for applications in fuel cells

  15. Pentafluorobenzene end-group as a versatile handle for para fluoro "click" functionalization of polythiophenes.

    Science.gov (United States)

    Boufflet, Pierre; Casey, Abby; Xia, Yiren; Stavrinou, Paul N; Heeney, Martin

    2017-03-01

    A convenient method of introducing pentafluorobenzene (PFB) as a single end-group in polythiophene derivatives is reported via in situ quenching of the polymerization. We demonstrate that the PFB-group is a particularly useful end-group due to its ability to undergo fast nucleophilic aromatic substitutions. Using this molecular handle, we are able to quantitatively tether a variety of common nucleophiles to the polythiophene backbone. The mild conditions required for the reaction allows sensitive functional moieties, such as biotin or a cross-linkable trimethoxysilane, to be introduced as end-groups. The high yield enabled the formation of a diblock rod-coil polymer from equimolar reactants under transition metal-free conditions at room temperature. We further demonstrate that water soluble polythiophenes end-capped with PFB can be prepared via the hydrolysis of an ester precursor, and that such polymers are amenable to functionalization under aqueous conditions.

  16. Femtosecond Pump-Push-Probe and Pump-Dump-Probe Spectroscopy of Conjugated Polymers: New Insight and Opportunities.

    Science.gov (United States)

    Kee, Tak W

    2014-09-18

    Conjugated polymers are an important class of soft materials that exhibit a wide range of applications. The excited states of conjugated polymers, often referred to as excitons, can either deactivate to yield the ground state or dissociate in the presence of an electron acceptor to form charge carriers. These interesting properties give rise to their luminescence and the photovoltaic effect. Femtosecond spectroscopy is a crucial tool for studying conjugated polymers. Recently, more elaborate experimental configurations utilizing three optical pulses, namely, pump-push-probe and pump-dump-probe, have been employed to investigate the properties of excitons and charge-transfer states of conjugated polymers. These studies have revealed new insight into femtosecond torsional relaxation and detrapping of bound charge pairs of conjugated polymers. This Perspective highlights (1) the recent achievements by several research groups in using pump-push-probe and pump-dump-probe spectroscopy to study conjugated polymers and (2) future opportunities and potential challenges of these techniques.

  17. Effect of backbone structure on charge transport along isolated conjugated polymer chains

    International Nuclear Information System (INIS)

    Siebbeles, Laurens D.A.; Grozema, Ferdinand C.; Haas, Matthijs P. de; Warman, John M.

    2005-01-01

    Fast charge transport in conjugated polymers is essential for their application in opto-electronic devices. In the present paper, measurements and theoretical modeling of the mobility of excess charges along isolated chains of conjugated polymers in dilute solution are presented. Charge carriers were produced by irradiation of the polymer solution with 3-MeV electrons from a Van de Graaff accelerator. The mobilities of the charges along the polymer chains were obtained from time-resolved microwave conductivity measurements. The mobilities are strongly dependent on the chemical nature of the polymer backbone. Comparison of the experimental data with results from ab initio quantum mechanical calculations shows that the measured mobilities are strongly limited by torsional disorder, chemical defects and chain ends. Improvement of the structure of polymer backbones is therefore expected to significantly enhance the performance of these materials in 'plastic electronics'

  18. Planar conjugated polymers containing 9,10-disubstituted phenanthrene units for efficient polymer solar cells.

    Science.gov (United States)

    Li, Guangwu; Kang, Chong; Li, Cuihong; Lu, Zhen; Zhang, Jicheng; Gong, Xue; Zhao, Guangyao; Dong, Huanli; Hu, Wenping; Bo, Zhishan

    2014-06-01

    Four novel conjugated polymers (P1-4) with 9,10-disubstituted phenanthrene (PhA) as the donor unit and 5,6-bis(octyloxy)benzothiadiazole as the acceptor unit are synthesized and characterized. These polymers are of medium bandgaps (2.0 eV), low-lying HOMO energy levels (below -5.3 eV), and high hole mobilities (in the range of 3.6 × 10(-3) to 0.02 cm(2) V(-1) s(-1) ). Bulk heterojunction (BHJ) polymer solar cells (PSCs) with P1-4:PC71 BM blends as the active layer and an alcohol-soluble fullerene derivative (FN-C60) as the interfacial layer between the active layer and cathode give the best power conversion efficiency (PCE) of 4.24%, indicating that 9,10-disubstituted PhA are potential donor materials for high-efficiency BHJ PSCs. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. Methyllithium-Doped Naphthyl-Containing Conjugated Microporous Polymer with Enhanced Hydrogen Storage Performance.

    Science.gov (United States)

    Xu, Dan; Sun, Lei; Li, Gang; Shang, Jin; Yang, Rui-Xia; Deng, Wei-Qiao

    2016-06-01

    Hydrogen storage is a primary challenge for using hydrogen as a fuel. With ideal hydrogen storage kinetics, the weak binding strength of hydrogen to sorbents is the key barrier to obtain decent hydrogen storage performance. Here, we reported the rational synthesis of a methyllithium-doped naphthyl-containing conjugated microporous polymer with exceptional binding strength of hydrogen to the polymer guided by theoretical simulations. Meanwhile, the experimental results showed that isosteric heat can reach up to 8.4 kJ mol(-1) and the methyllithium-doped naphthyl-containing conjugated microporous polymer exhibited an enhanced hydrogen storage performance with 150 % enhancement compared with its counterpart naphthyl-containing conjugated microporous polymer. These results indicate that this strategy provides a direction for design and synthesis of new materials that meet the US Department of Energy (DOE) hydrogen storage target. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  20. Design, synthesis and photovoltaic properties of a series of new acceptor-pended conjugated polymers

    Institute of Scientific and Technical Information of China (English)

    Zhihong; Wu; Yongxiang; Zhu; Wei; Li; Yunping; Huang; Junwu; Chen; Chunhui; Duan; Fei; Huang; Yong; Cao

    2016-01-01

    A series of novel acceptor-pended conjugated polymers featuring a newly developed carbazole-derived unit are designed and synthesized. The relationships between chemical structure and optoelectronic properties of the polymers are systematically investigated.The control of UV-Vis absorption spectra and energy levels in resulting polymers are achieved by introducing suitable pended acceptor units. The photovoltaic properties of the resulting polymers are evaluated by blending the polymers with(6,6)-phenyl-C71-butyric acid methyl ester. The resulting solar cells exhibit moderate performances with high open-circuit voltage. Charge transport properties and morphology were investigated to understand the performance of corresponding solar cells.

  1. Structural and electrochemical properties of polythiophene

    Energy Technology Data Exchange (ETDEWEB)

    Senthilkumar, B.; Thenamirtham, P. [Solid State Ionics and Energy Devices Laboratory, Department of Physics, Bharathiar University, Coimbatore 641 046 (India); Kalai Selvan, R., E-mail: selvankram@buc.edu.in [Solid State Ionics and Energy Devices Laboratory, Department of Physics, Bharathiar University, Coimbatore 641 046 (India)

    2011-08-15

    Polythiophenes (PTs) were prepared by chemical oxidative polymerization method in presence and absence of three different (cationic - CTAB, anionic - SDS and non-ionic - Triton X-100) surfactants using FeCl{sub 3} as oxidant. The prepared PTs were characterized by FT-IR, UV-Vis, XRD, SEM and cyclic voltammetry studies. The FT-IR spectra inferred the polymerization of thiophene and elucidate the corresponding functional groups of PTs. Our results on the UV-Vis spectra demonstrate the n-{pi}* electronic transition of the conjugated molecules. Further the red shift in the absorption peak confirms the longer conjugation length of PTs. The amorphous nature of the PTs was inferred from the XRD pattern. The PTs prepared with surfactant exhibited different morphology compared to PT prepared without surfactant. The specific capacitances (SC) of the prepared PTs were calculated using cyclic voltammetry technique, the PT prepared with TRITRON X-100 exhibited higher SC of 117 F/g compared to SC of surfactant free PT (78 F/g). Hence, the PTs prepared with surfactants were found to be suitable electrode materials for redox supercapacitors.

  2. Thiolated polymers--thiomers: development and in vitro evaluation of chitosan-thioglycolic acid conjugates.

    Science.gov (United States)

    Kast, C E; Bernkop-Schnürch, A

    2001-09-01

    The aim of this study was to improve mucoadhesive properties of chitosan by the covalent attachment of thiol moieties to this cationic polymer. Mediated by a carbodiimide, thioglycolic acid (TGA) was covalently attached to chitosan. This was achieved by the formation of amide bonds between the primary amino groups of the polymer and the carboxylic acid group of TGA. Dependent on the pH-value and the weight ratio of polymer to TGA during the coupling reaction the resulting thiolated polymers, the so-called thiomers, displayed 6.58, 9.88, 27.44, and 38.23 micromole thiol groups per gram polymer. Tensile studies carried out with these chitosan-TGA conjugates on freshly excised porcine intestinal mucosa demonstrated a 6.3-, 8.6-, 8.9-, and 10.3-fold increase in the total work of adhesion (TWA) compared to the unmodified polymer, respectively. In contrast, the combination of chitosan and free unconjugated TGA showed almost no mucoadhesion. These data were in good correlation with further results obtained by another mucoadhesion test demonstrating a prolonged residence time of thiolated chitosan on porcine mucosa. The swelling behavior of all conjugates was thereby exactly in the same range as for an unmodified polymer pretreated in the same way. Furthermore, it could be shown that chitosan-TGA conjugates are still biodegradable by the glycosidase lysozyme. According to these results. chitosan-TGA conjugates represent a promising tool for the development of mucoadhesive drug delivery systems.

  3. π-Conjugated polymer anisotropic organogel nanofibrous assemblies for thermoresponsive photonic switches.

    Science.gov (United States)

    Narasimha, Karnati; Jayakannan, Manickam

    2014-11-12

    The present work demonstrates one of the first examples of π-conjugated photonic switches (or photonic wave plates) based on the tailor-made π-conjugated polymer anisotropic organogel. New semicrystalline segmented π-conjugated polymers are designed with rigid aromatic oligophenylenevinylene π-core and flexible alkyl chain along the polymer backbone. These polymers are found to be self-assembled as semicrystalline or amorphous with respect to the number of carbon atoms in the alkyl units. These semicrystalline polymers produce organogels having nanofibrous morphology of 20 nm thickness with length up to 5 μm. The polymer organogel is aligned in a narrow glass capillary, and this anisotropic gel device is further demonstrated as photonic switches. The glass capillary device behaves as typical λ/4 photonic wave plates upon the illumination of the plane polarized light. The λ/4 photonic switching ability is found to be maximum at θ = 45° angle under the cross polarizers. The orthogonal arrangements of the gel capillaries produce dark and bright spots as on-and-off optical switches. Thermoreversibility of the polymer organogel (also its xerogel) was exploited to construct thermoresponsive photonic switches for the temperature window starting from 25 to 160 °C. The organic photonic switch concept can be adapted to large number of other π-conjugated materials for optical communication and storage.

  4. Functional Hybrid Biomaterials based on Peptide-Polymer Conjugates for Nanomedicine

    Science.gov (United States)

    Shu, Jessica Yo

    The focus of this dissertation is the design, synthesis and characterization of hybrid functional biomaterials based on peptide-polymer conjugates for nanomedicine. Generating synthetic materials with properties comparable to or superior than those found in nature has been a "holy grail" for the materials community. Man-made materials are still rather simplistic when compared to the chemical and structural complexity of a cell. Peptide-polymer conjugates have the potential to combine the advantages of the biological and synthetic worlds---that is they can combine the precise chemical structure and diverse functionality of biomolecules with the stability and processibility of synthetic polymers. As a new family of soft matter, they may lead to materials with novel properties that have yet to be realized with either of the components alone. In order for peptide-polymer conjugates to reach their full potential as useful materials, the structure and function of the peptide should be maintained upon polymer conjugation. The success in achieving desirable, functional assemblies relies on fundamentally understanding the interactions between each building block and delicately balancing and manipulating these interactions to achieve targeted assemblies without interfering with designed structures and functionalities. Such fundamental studies of peptide-polymer interactions were investigated as the nature of the polymer (hydrophilic vs. hydrophobic) and the site of its conjugation (end-conjugation vs. side-conjugation) were varied. The fundamental knowledge gained was then applied to the design of amphiphiles that self-assemble to form stable functional micelles. The micelles exhibited exceptional monodispersity and long-term stability, which is atypical of self-assembled systems. Thus such micelles based on amphiphilic peptide-polymer conjugates may meet many current demands in nanomedicine, in particular for drug delivery of hydrophobic anti-cancer therapeutics. Lastly

  5. Micelle-like nanoassemblies based on polymer-drug conjugates as an emerging platform for drug delivery.

    Science.gov (United States)

    Liu, Zhihong; Wang, Yutao; Zhang, Na

    2012-07-01

    During the past decades, polymer-drug conjugates are one of the hottest topics in novel drug development fields. Amphiphilic polymer-drug conjugates in aqueous solution could form micelles or micelle-like nanoassemblies. Compared with polymer-drug conjugates and the micelles into which drugs are physically entrapped, micelles or micelle-like nanoassemblies based on polymer-drug conjugates bring several additional advantages, including increased drug-loading capacity, enhanced intracellular uptake, reduced systemic toxicity, and improved therapeutic efficacy. This review focuses on recent progress achieved in the research field of micelles or micelle-like nanoassemblies based on polymer-drug conjugates. Firstly, properties of polymers, drugs, and linkers which could be used to build polymer-drug conjugate micelles or micelle-like nanoassemblies are summarized. Then, the characterization methods are described. Finally, the drug-targeting mechanisms are discussed. Micelles or micelle-like nanoassemblies based on polymer-drug conjugates as an emerging platform have the potential to achieve medical treatments with enhanced therapeutic effect. The application of micelles or micelle-like nanoassemblies based on polymer-drug conjugates may give new life to old active compounds abandoned due to their low solubility problems. For clinical application, there is a need to further optimize the properties of the polymer, drug, and linker.

  6. Photoinduced FT-IR spectroscopy and CW-photocurrent measurements of conjugated polymers and fullerenes blended into a conventional polymer matrix

    NARCIS (Netherlands)

    Brabec, C.J.; Johannson, H.; Padinger, F.; Neugebauer, H.; Hummelen, J.C.; Sariciftci, N.S.

    2000-01-01

    In this work we present an investigation of the photoexcited states in conjugated polymer (donor) - fullerene (acceptor) interpenetrating networks embedded into conventional polymer hosts like polystyrene (PS), polyvinylcarbazole (PVK) or polyvinylbenzylchloride (PVBC) (guest - host approach), using

  7. Nanostructured Conjugated Polymers for Energy-Related Applications beyond Solar Cells.

    Science.gov (United States)

    Xie, Jian; Zhao, Cui-E; Lin, Zong-Qiong; Gu, Pei-Yang; Zhang, Qichun

    2016-05-20

    To meet the ever-increasing requirements for the next generation of sustainable and versatile energy-related devices, conjugated polymers, which have potential advantages over small molecules and inorganic materials, are among the most promising types of green candidates. The properties of conjugated polymers can be tuned through modification of the structure and incorporation of different functional moieties. In addition, superior performances can be achieved as a result of the advantages of nanostructures, such as their large surface areas and the shortened pathways for charge transfer. Therefore, nanostructured conjugated polymers with different properties can be obtained to be applied in different energy-related organic devices. This review focuses on the application and performance of the recently reported nanostructured conjugated polymers for high-performance devices, including rechargeable lithium batteries, microbial fuel cells (MFCs), thermoelectric generators, and photocatalytic systems. The design strategies, reaction mechanisms, advantages, and limitations of nanostructured conjugated polymers are further discussed in each section. Finally, possible routes to improve the performances of the current systems are also included in the conclusion. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. Nature of the Binding Interactions between Conjugated Polymer Chains and Fullerenes in Bulk Heterojunction Organic Solar Cells

    KAUST Repository

    Ravva, Mahesh Kumar; Wang, Tonghui; Bredas, Jean-Luc

    2016-01-01

    Blends of π-conjugated polymers and fullerene derivatives are ubiquitous as the active layers of organic solar cells. However, a detailed understanding of the weak noncovalent interactions at the molecular level between the polymer chains

  9. Vinyl Flanked Difluorobenzothiadiazole-Dithiophene Conjugated Polymer for High Performance Organic Field-Effect Transistors.

    Energy Technology Data Exchange (ETDEWEB)

    Liang, Xianfeng; Sun, Wandong; Chen, Yanlin; Tan, Luxi; Cai, Zheng-Xu; Liu, Zitong; Wang, Lin; Li, Jing; Chen, Wei; Dong, Lichun

    2018-02-21

    Fluorine containing conjugated polymers have been widely applied in high performance organic solar cells, but their use in field-effect transistors is still quite limited. In this work, a conjugated polymer PTFBTV based on difluorobenzothiadiazole (DFBT) and dithiophene was synthesized, utilizing multiple vinylene as linkers. The polymer exhibits a relatively high hole mobility up to 2.0 cm(2) V-1 s(-1) compared with the reported DFBT-oligothiophene based polymers, yet its structural complexity is much simpler. The polymer thin film exhibits a typical 'face on' molecular orientation. A single crystal of its monomer revealed a non-covalent intramolecular contact between fluorine and the neighbouring proton, which strengthens the backbone co-planarity. Meanwhile an intermolecular F...F contact was also observed, which might cause rather scattered lamellar crystallinity for PTFBTV in the solid state.

  10. Impact of the Crystallite Orientation Distribution on Exciton Transport in Donor–Acceptor Conjugated Polymers

    KAUST Repository

    Ayzner, Alexander L.

    2015-12-30

    © 2015 American Chemical Society. Conjugated polymers are widely used materials in organic photovoltaic devices. Owing to their extended electronic wave functions, they often form semicrystalline thin films. In this work, we aim to understand whether distribution of crystallographic orientations affects exciton diffusion using a low-band-gap polymer backbone motif that is representative of the donor/acceptor copolymer class. Using the fact that the polymer side chain can tune the dominant crystallographic orientation in the thin film, we have measured the quenching of polymer photoluminescence, and thus the extent of exciton dissociation, as a function of crystal orientation with respect to a quenching substrate. We find that the crystallite orientation distribution has little effect on the average exciton diffusion length. We suggest several possibilities for the lack of correlation between crystallographic texture and exciton transport in semicrystalline conjugated polymer films.

  11. Impact of the Crystallite Orientation Distribution on Exciton Transport in Donor–Acceptor Conjugated Polymers

    KAUST Repository

    Ayzner, Alexander L.; Mei, Jianguo; Appleton, Anthony; DeLongchamp, Dean; Nardes, Alexandre; Benight, Stephanie; Kopidakis, Nikos; Toney, Michael F.; Bao, Zhenan

    2015-01-01

    © 2015 American Chemical Society. Conjugated polymers are widely used materials in organic photovoltaic devices. Owing to their extended electronic wave functions, they often form semicrystalline thin films. In this work, we aim to understand whether distribution of crystallographic orientations affects exciton diffusion using a low-band-gap polymer backbone motif that is representative of the donor/acceptor copolymer class. Using the fact that the polymer side chain can tune the dominant crystallographic orientation in the thin film, we have measured the quenching of polymer photoluminescence, and thus the extent of exciton dissociation, as a function of crystal orientation with respect to a quenching substrate. We find that the crystallite orientation distribution has little effect on the average exciton diffusion length. We suggest several possibilities for the lack of correlation between crystallographic texture and exciton transport in semicrystalline conjugated polymer films.

  12. CONJUGATED POLYMERS AND POLYELECTROLYTES IN SOLAR PHOTOCONVERSION, Final Technical Report

    Energy Technology Data Exchange (ETDEWEB)

    Schanze, Kirk S [University of Florida

    2014-08-05

    This DOE-supported program investigated the fundamental properties of conjugated polyelectrolytes, with emphasis placed on studies of excited state energy transport, self-assembly into conjugated polyelectroyte (CPE) based films and colloids, and exciton transport and charge injection in CPE films constructed atop wide bandgap semiconductors. In the most recent grant period we have also extended efforts to examine the properties of low-bandgap donor-acceptor conjugated polyelectrolytes that feature strong visible light absorption and the ability to adsorb to metal-oxide interfaces.

  13. Tunable Semiconducting Polymer Nanoparticles with INDT-Based Conjugated Polymers for Photoacoustic Molecular Imaging.

    Science.gov (United States)

    Stahl, Thomas; Bofinger, Robin; Lam, Ivan; Fallon, Kealan J; Johnson, Peter; Ogunlade, Olumide; Vassileva, Vessela; Pedley, R Barbara; Beard, Paul C; Hailes, Helen C; Bronstein, Hugo; Tabor, Alethea B

    2017-06-21

    Photoacoustic imaging combines both excellent spatial resolution with high contrast and specificity, without the need for patients to be exposed to ionizing radiation. This makes it ideal for the study of physiological changes occurring during tumorigenesis and cardiovascular disease. In order to fully exploit the potential of this technique, new exogenous contrast agents with strong absorbance in the near-infrared range, good stability and biocompatibility, are required. In this paper, we report the formulation and characterization of a novel series of endogenous contrast agents for photoacoustic imaging in vivo. These contrast agents are based on a recently reported series of indigoid π-conjugated organic semiconductors, coformulated with 1,2-dipalmitoyl-sn-glycero-3-phosphocholine, to give semiconducting polymer nanoparticles of about 150 nm diameter. These nanoparticles exhibited excellent absorption in the near-infrared region, with good photoacoustic signal generation efficiencies, high photostability, and extinction coefficients of up to three times higher than those previously reported. The absorption maximum is conveniently located in the spectral region of low absorption of chromophores within human tissue. Using the most promising semiconducting polymer nanoparticle, we have demonstrated wavelength-dependent differential contrast between vasculature and the nanoparticles, which can be used to unambiguously discriminate the presence of the contrast agent in vivo.

  14. Novel Luminescent Multilayer Films Containing π-Conjugated Anionic Polymer with Electronic Microenvironment

    Directory of Open Access Journals (Sweden)

    Tianlei Wang

    2016-09-01

    Full Text Available Layered double hydroxides (LDHs, luminescent π-conjugated anionic polymer and montmorillonite (MMT were orderly assembled into luminescent multilayer films via layer-by-layer self-assembly method. The electronic microenvironment (EME, the structure of which is like a traditional capacitor, can be constructed by exfoliated LDHs or MMT nanosheets. In addition, the rigid inorganic laminated configuration can offer stable surroundings between the interlayers. As a result, we conclude that EME can extend the luminescent lifespans of multilayer films substantially, due to affecting relaxation times of π-conjugated anionic polymer. Consequently, because of the remarkable impact on better photoemission behaviors of luminescent π-conjugated anionic polymer, EME assembled by LDHs or MMT nanosheets have had high hopes attached to them. They are expected to have the potential for designing, constructing, and investigating novel light-emitting thin films.

  15. Singlet Exciton Lifetimes in Conjugated Polymer Films for Organic Solar Cells

    KAUST Repository

    Dimitrov, Stoichko

    2016-01-13

    The lifetime of singlet excitons in conjugated polymer films is a key factor taken into account during organic solar cell device optimization. It determines the singlet exciton diffusion lengths in polymer films and has a direct impact on the photocurrent generation by organic solar cell devices. However, very little is known about the material properties controlling the lifetimes of singlet excitons, with most of our knowledge originating from studies of small organic molecules. Herein, we provide a brief summary of the nature of the excited states in conjugated polymer films and then present an analysis of the singlet exciton lifetimes of 16 semiconducting polymers. The exciton lifetimes of seven of the studied polymers were measured using ultrafast transient absorption spectroscopy and compared to the lifetimes of seven of the most common photoactive polymers found in the literature. A plot of the logarithm of the rate of exciton decay vs. the polymer optical bandgap reveals a medium correlation between lifetime and bandgap, thus suggesting that the Energy Gap Law may be valid for these systems. This therefore suggests that small bandgap polymers can suffer from short exciton lifetimes, which may limit their performance in organic solar cell devices. In addition, the impact of film crystallinity on the exciton lifetime was assessed for a small bandgap diketopyrrolopyrrole co-polymer. It is observed that the increase of polymer film crystallinity leads to reduction in exciton lifetime and optical bandgap again in agreement with the Energy Gap Law.

  16. In situ measurements of the optical absorption of dioxythiophene-based conjugated polymers

    Science.gov (United States)

    Hwang, J.; Schwendeman, I.; Ihas, B. C.; Clark, R. J.; Cornick, M.; Nikolou, M.; Argun, A.; Reynolds, J. R.; Tanner, D. B.

    2011-05-01

    Conjugated polymers can be reversibly doped by electrochemical means. This doping introduces new subband-gap optical absorption bands in the polymer while decreasing the band-gap absorption. To study this behavior, we have prepared an electrochemical cell allowing in situ measurements of the optical properties of the polymer. The cell consists of a thin polymer film deposited on gold-coated Mylar behind which is another polymer that serves as a counterelectrode. An infrared transparent window protects the upper polymer from ambient air. By adding a gel electrolyte and making electrical connections to the polymer-on-gold films, one may study electrochromism in a wide spectral range. As the cell voltage (the potential difference between the two electrodes) changes, the doping level of the conjugated polymer films is changed reversibly. Our experiments address electrochromism in poly(3,4-ethylenedioxythiophene) (PEDOT) and poly(3,4-dimethylpropylenedioxythiophene) (PProDOT-Me2). This closed electrochemical cell allows the study of the doping induced subband-gap features (polaronic and bipolaronic modes) in these easily oxidized and highly redox switchable polymers. We also study the changes in cell spectra as a function of polymer thickness and investigate strategies to obtain cleaner spectra, minimizing the contributions of water and gel electrolyte features.

  17. Synthesis and characterization of polythiophene-modified TiO2 ...

    Indian Academy of Sciences (India)

    prospects and has attracted much attention for its many advantages such as ... the ground state of the polymer located in the semiconduc- tor energy gap into an .... in figure 1(c) that the polythiophene modified TiO2 nanotube arrays still keep ...

  18. Near-infrared (NIR) emitting conjugated polymers for biomedical applications (Presentation Recording)

    Science.gov (United States)

    Repenko, Tatjana; Kuehne, Alexander J. C.

    2015-10-01

    Fluorescent biomedical markers of today such as dye-infiltrated colloids, microgels and quantum dots suffer from fast bleaching, lack surface functionality (for targets or pharmaceutical agents) and potentially leach heavy metals in case of quantum dots (e.g. Cd). By contrast, conjugated polymer particles are non-cytotoxic, exhibit reduced bleaching, as the entire particle consists of fluorophore, they are hydrophobic and show high quantum yields. Consequently, conjugated polymer particles represent ideal materials for biological applications and imaging. However currently, conjugated polymer particles for biomedical imaging usually lack near-infrared (NIR) emission and are polydisperse. Fluorescent agents with emission in the NIR spectrum are interesting for biomedical applications due to their low photo-damage towards biological species and the ability of NIR radiation to penetrate deep into biological tissue.. I will present the development and synthesis of new conjugated polymers particles with fluorescence in the NIR spectral region for bio-imaging and clinical diagnosis. The particle synthesis proceeds in a one-step Pd or Ni-catalyzed dispersion polymerization of functional NIR emitters. The resulting monodisperse conjugated polymer particles are obtained as a dispersion in a non-hazardous solvent. Different sizes in the sub-micrometer range with a narrow size distribution can be produced. Furthermore biological recognition motifs can be easily attached to the conjugated polymers via thiol-yne click-chemistry providing specific tumor targeting without quenching of the fluorescence. References [1] Kuehne AJC, Gather MC, Sprakel J., Nature Commun. 2012, 3, 1088. [2] Repenko T, Fokong S, De Laporte L, Go D, Kiessling F, Lammers T, Kuehne AJC.,Chem Commun 2015, accepted.

  19. Synthesis and photocatalytic activity of TiO2/conjugated polymer complex nanoparticles

    Institute of Scientific and Technical Information of China (English)

    Shi Xiong Min; Fang Wang; Lei Feng; Yong Chun Tong; Zi Rong Yang

    2008-01-01

    A photocatalyst of nanometer TiO2/conjugated polymer complex was successfully synthesized and characterized by spectroscopic methods and photocatalytic experiments. The complex photocatalyst could be activated by absorbing both ultraviolet and visible light (λ=190-800nm). Methylene blue (MB) could be degraded more efficiently on the complex photocatalyst than on the TiO2 under natural light. The conjugated polymer played a promoting role in the photocatalytic degradation of MB. The calcination temperature had an important effect in degradation of dye and could be summarized as 260℃>300℃>340℃>220℃>180℃.

  20. Impact of morphology on polaron delocalization in a semicrystalline conjugated polymer

    KAUST Repository

    Steyrleuthner, Robert

    2016-12-20

    We investigate the delocalization of holes in the semicrystalline conjugated polymer poly(2,5-bis(3-alkylthiophene-2-yl)thieno[3,2-b]thiophene) (PBTTT) by directly measuring the hyperfine coupling between photogenerated polarons and bound nuclear spins using electron nuclear double resonance spectroscopy. An extrapolation of the corresponding oligomer spectra reveals that charges tend to delocalize over 4.0-4.8 nm with delocalization strongly dependent on molecular order and crystallinity of the PBTTT polymer thin films. Density functional theory calculations of hyperfine couplings confirm that long-range corrected functionals appropriately describe the change in coupling strength with increasing oligomer size and agree well with the experimentally measured polymer limit. Our discussion presents general guidelines illustrating the various pitfalls and opportunities when deducing polaron localization lengths from hyperfine coupling spectra of conjugated polymers.

  1. A general relationship between disorder, aggregation and charge transport in conjugated polymers

    KAUST Repository

    Noriega, Rodrigo

    2013-08-04

    Conjugated polymer chains have many degrees of conformational freedom and interact weakly with each other, resulting in complex microstructures in the solid state. Understanding charge transport in such systems, which have amorphous and ordered phases exhibiting varying degrees of order, has proved difficult owing to the contribution of electronic processes at various length scales. The growing technological appeal of these semiconductors makes such fundamental knowledge extremely important for materials and process design. We propose a unified model of how charge carriers travel in conjugated polymer films. We show that in high-molecular-weight semiconducting polymers the limiting charge transport step is trapping caused by lattice disorder, and that short-range intermolecular aggregation is sufficient for efficient long-range charge transport. This generalization explains the seemingly contradicting high performance of recently reported, poorly ordered polymers and suggests molecular design strategies to further improve the performance of future generations of organic electronic materials. © 2013 Macmillan Publishers Limited. All rights reserved.

  2. A general relationship between disorder, aggregation and charge transport in conjugated polymers

    KAUST Repository

    Noriega, Rodrigo; Rivnay, Jonathan; Vandewal, Koen; Koch, Felix P. V.; Stingelin, Natalie; Smith, Paul; Toney, Michael F.; Salleo, Alberto

    2013-01-01

    Conjugated polymer chains have many degrees of conformational freedom and interact weakly with each other, resulting in complex microstructures in the solid state. Understanding charge transport in such systems, which have amorphous and ordered phases exhibiting varying degrees of order, has proved difficult owing to the contribution of electronic processes at various length scales. The growing technological appeal of these semiconductors makes such fundamental knowledge extremely important for materials and process design. We propose a unified model of how charge carriers travel in conjugated polymer films. We show that in high-molecular-weight semiconducting polymers the limiting charge transport step is trapping caused by lattice disorder, and that short-range intermolecular aggregation is sufficient for efficient long-range charge transport. This generalization explains the seemingly contradicting high performance of recently reported, poorly ordered polymers and suggests molecular design strategies to further improve the performance of future generations of organic electronic materials. © 2013 Macmillan Publishers Limited. All rights reserved.

  3. Photoinduced partial charge transfer between conjugated polymer and fullerene in solutions

    International Nuclear Information System (INIS)

    Lin Hongzhen; Weng Yufeng; Huang Hongmin; He Qingguo; Zheng Min; Bai Fenglian

    2004-01-01

    Photoinduced charge transfer between a conjugated polymer and C 60 and the related processes were investigated in dilute solutions. The substantial fluorescence quenching is correlated with the efficient exciton diffusion within the polymer chains, according to which a sphere-of-action mechanism is proposed. An emissive exciplex was found formed between the conjugated polymer and fullerene in a nonpolar solvent, indicating the occurrence of a photoinduced partial charge transfer process. The low-energy sites in the polymer are believed to play a crucial role in the partial charge transfer. The asymmetry of the exciplex provides a method for evaluating the tendency of photoinduced charge separation between the donor and the acceptor. This method allows screening candidates for photovoltaic applications

  4. Spectral Signatures of Polarons in Conjugated Co-polymers

    NARCIS (Netherlands)

    Wiebeler, Christian; Tautz, Raphael; Feldmann, Jochen; von Hauff, Elizabeth; Da Como, Enrico; Schumacher, Stefan

    2013-01-01

    We study electronic and optical properties of the low-bandgap co-polymer PCPDT-BT (poly-cyclopentadithiophene-co-benzothiadiazole) and compare it with the corresponding homo-polymer PCPDT (poly-cyclopentadithiophene). We investigate the linear absorptivity in these systems for neutral molecules and

  5. Generation of native polythiophene/PCBM composite nanoparticles via the combination of ultrasonic micronization of droplets and thermocleaving from aqueous dispersion

    DEFF Research Database (Denmark)

    Nan, Yaxiong; Hu, Xiaolian; Larsen-Olsen, Thue Trofod

    2011-01-01

    -PT/PCBM nanoparticles were determined by atomic force microscopy (AFM), small-angle x-ray scattering (SAXS) and grazing incidence SAXS (GISAXS), giving an average size of ~ 140 nm. The GISAXS results reveal that n-PT/PCBM nanoparticles pack in an ordered structure as opposed to the P3MHOCT/PCBM nanoparticles......We report the preparation of native polythiophene (n-PT)/[6, 6]-phenyl-C61-butyric acid methyl ester (PCBM) composite nanoparticles from a poly[3-(2-methylhex-2-yl)oxy-carbonyldithiophene] (P3MHOCT)/PCBM aqueous dispersion prepared from an ultrasonically generated emulsion. The subsequent steps....... The successful vapour-phase preparation of phase-separated n-PT/PCBM nanoparticles provides a new route to all-aqueous processing of conjugated materials relevant to efficient polymer solar cells with long operational stability. The use of ultrasound was involved in both liquid and gas phases demonstrating...

  6. Photovoltaic cells made from conjugated polymers infiltrated into ordered nanoporous hosts

    Science.gov (United States)

    Coakley, Kevin M.

    Semiconducting (conjugated) polymers have several properties which make them ideal candidates for use in low-cost photovoltaic (PV) cells, including their typically high (105 cm-1) optical absorption coefficients, their ability to be cast from solution using a variety of wet-processing techniques, and the ability to tune their band gap. While most approaches for making conjugated polymer-based PV cells involve randomly intermixing the polymers with electron acceptors that act as sites for exciton dissociation, we have sought to obtain a more optimized morphology of the blended materials through a self-assembly technique. In the first half of this dissertation, we describe our preliminary attempts to make PV cells from conjugated polymers infiltrated into a self-assembled mesoporous titanic (TiO 2) electron acceptor that is ordered on the nanometer length scale. We first present a procedure for fabricating films of mesoporous TiO 2 and then show how its pores can be filled with a conjugated polymer, regioregular poly(3-hexylthiophene) (P3HT). In these films we have achieved precise control of the morphology of the two materials that has not yet been achieved elsewhere. However, as discussed subsequently, the photovoltaic performance of these films has not yet reached the level achieved by other types of conjugated polymer-based PV cells, with a maximum achieved power efficiency of approximately 0.45%. In the second half of this dissertation, we embark on a more fundamental study of the materials requirements for efficient polymer photovoltaics, including models that show how the maximum achievable power efficiency is limited by energy loss during forward electron transfer, and how the maximum achievable photocurrent is limited by the limiting carrier mobility and back electron transfer. Our modeling suggests that, for a back recombination time constant of 1 mus, a limiting carrier mobility of 10-3--10 -2 cm2/Vs is required in order to achieve a large photocurrent

  7. Regioregular narrow-bandgap-conjugated polymers for plastic electronics

    Science.gov (United States)

    Ying, Lei; Huang, Fei; Bazan, Guillermo C.

    2017-03-01

    Progress in the molecular design and processing protocols of semiconducting polymers has opened significant opportunities for the fabrication of low-cost plastic electronic devices. Recent studies indicate that field-effect transistors and organic solar cells fabricated using narrow-bandgap regioregular polymers with translational symmetries in the direction of the backbone vector often outperform those containing analogous regiorandom polymers. This review addresses the cutting edge of regioregularity chemistry, in particular how to control the spatial distribution in the molecular structures and how this order translates to more ordered bulk morphologies. The effect of regioregularity on charge transport and photovoltaic properties is also outlined.

  8. New electroluminescent carbazole-containing conjugated polymer: synthesis, photophysics, and electroluminescence

    Czech Academy of Sciences Publication Activity Database

    Cimrová, Věra; Ulbricht, C.; Dzhabarov, Vagif; Výprachtický, Drahomír; Egbe, D. A. M.

    2014-01-01

    Roč. 55, č. 24 (2014), s. 6220-6226 ISSN 0032-3861 R&D Projects: GA ČR GAP106/12/0827; GA ČR(CZ) GA13-26542S Institutional support: RVO:61389013 Keywords : carbazole-containing conjugated polymer * synthesis * photophysics and electroluminescence Subject RIV: CD - Macromolecular Chemistry Impact factor: 3.562, year: 2014

  9. Pluronic-lysozyme conjugates as anti-adhesive and antibacterial bifunctional polymers for surface coating

    NARCIS (Netherlands)

    Muszanska, A.K.; Busscher, H.J.; Herrmann, A.; Mei, van der H.C.; Norde, W.

    2011-01-01

    This paper describes the preparation and characterization of polymer protein conjugates composed of a synthetic triblock copolymer with a central polypropylene oxide (PPO) block and two terminal polyethylene oxide (PEO) segments, Pluronic F-127, and the antibacterial enzyme lysozyme attached to the

  10. Impact of morphology on polaron delocalization in a semicrystalline conjugated polymer

    KAUST Repository

    Steyrleuthner, Robert; Zhang, Yuexing; Zhang, Lei; Kraffert, Felix; Cherniawski, Benjamin P.; Bittl, Robert; Briseno, Alejandro L.; Bredas, Jean-Luc; Behrends, Jan

    2016-01-01

    We investigate the delocalization of holes in the semicrystalline conjugated polymer poly(2,5-bis(3-alkylthiophene-2-yl)thieno[3,2-b]thiophene) (PBTTT) by directly measuring the hyperfine coupling between photogenerated polarons and bound nuclear

  11. Stability issues of conjugated polymer / fullerene solar cells from a chemical viewpoint

    NARCIS (Netherlands)

    Hummelen, J.C.; Knol, J.; Sánchez, L.

    2001-01-01

    The efficiency of energy conversion and the stability or lifetime of ‘plastic’ photovoltaic cells, based on conjugated polymer/ fullerene blends, are the two main issues to be improved for this type of devices. The stability of these PV cells depends potentially on a large number of factors. A brief

  12. Dual-Color Fluorescence Imaging of Magnetic Nanoparticles in Live Cancer Cells Using Conjugated Polymer Probes

    Science.gov (United States)

    Sun, Minjie; Sun, Bin; Liu, Yun; Shen, Qun-Dong; Jiang, Shaojun

    2016-01-01

    Rapid growth in biological applications of nanomaterials brings about pressing needs for exploring nanomaterial-cell interactions. Cationic blue-emissive and anionic green-emissive conjugated polymers are applied as dual-color fluorescence probes to the surface of negatively charged magnetic nanoparticles through sequentially electrostatic adsorption. These conjugated polymers have large extinction coefficients and high fluorescence quantum yield (82% for PFN and 62% for ThPFS). Thereby, one can visualize trace amount (2.7 μg/mL) of fluorescence-labeled nanoparticles within cancer cells by confocal laser scanning microscopy. Fluorescence labeling by the conjugated polymers is also validated for quantitative determination of the internalized nanoparticles in each individual cell by flow cytometry analysis. Extensive overlap of blue and green fluorescence signals in the cytoplasm indicates that both conjugated polymer probes tightly bind to the surface of the nanoparticles during cellular internalization. The highly charged and fluorescence-labeled nanoparticles non-specifically bind to the cell membranes, followed by cellular uptake through endocytosis. The nanoparticles form aggregates inside endosomes, which yields a punctuated staining pattern. Cellular internalization of the nanoparticles is dependent on the dosage and time. Uptake efficiency can be enhanced three-fold by application of an external magnetic field. The nanoparticles are low cytotoxicity and suitable for simultaneously noninvasive fluorescence and magnetic resonance imaging application. PMID:26931282

  13. Developments in the chemistry and band gap engineering of donor-acceptor substituted conjugated polymers

    NARCIS (Netherlands)

    Mullekom, van H.A.M.; Vekemans, J.A.J.M.; Havinga, E.E.; Meijer, E.W.

    2001-01-01

    This paper reviews the tools to manipulate and minimize the band gap of conjugated (co)polymers. The effects of minimization of the bond length alternation and of the incorporation of donor-K-acceptor units are discussed in particular. A systematic study of a series of alternating donor-acceptor

  14. Comparison of eosin and fluorescein conjugates for the photoinitiation of cell-compatible polymer coatings.

    Directory of Open Access Journals (Sweden)

    Jacob L Lilly

    Full Text Available Targeted photopolymerization is the basis for multiple diagnostic and cell encapsulation technologies. While eosin is used in conjunction with tertiary amines as a water-soluble photoinitiation system, eosin is not widely sold as a conjugate with antibodies and other targeting biomolecules. Here we evaluate the utility of fluorescein-labeled bioconjugates to photopolymerize targeted coatings on live cells. We show that although fluorescein conjugates absorb approximately 50% less light energy than eosin in matched photopolymerization experiments using a 530 nm LED lamp, appreciable polymer thicknesses can still be formed in cell compatible environments with fluorescein photosensitization. At low photoinitiator density, eosin allows more sensitive initiation of gelation. However at higher functionalization densities, the thickness of fluorescein polymer films begins to rival that of eosin. Commercial fluorescein-conjugated antibodies are also capable of generating conformal, protective coatings on mammalian cells with similar viability and encapsulation efficiency as eosin systems.

  15. Comparison of eosin and fluorescein conjugates for the photoinitiation of cell-compatible polymer coatings.

    Science.gov (United States)

    Lilly, Jacob L; Gottipati, Anuhya; Cahall, Calvin F; Agoub, Mohamed; Berron, Brad J

    2018-01-01

    Targeted photopolymerization is the basis for multiple diagnostic and cell encapsulation technologies. While eosin is used in conjunction with tertiary amines as a water-soluble photoinitiation system, eosin is not widely sold as a conjugate with antibodies and other targeting biomolecules. Here we evaluate the utility of fluorescein-labeled bioconjugates to photopolymerize targeted coatings on live cells. We show that although fluorescein conjugates absorb approximately 50% less light energy than eosin in matched photopolymerization experiments using a 530 nm LED lamp, appreciable polymer thicknesses can still be formed in cell compatible environments with fluorescein photosensitization. At low photoinitiator density, eosin allows more sensitive initiation of gelation. However at higher functionalization densities, the thickness of fluorescein polymer films begins to rival that of eosin. Commercial fluorescein-conjugated antibodies are also capable of generating conformal, protective coatings on mammalian cells with similar viability and encapsulation efficiency as eosin systems.

  16. Toward High Performance Photovoltaic Cells based on Conjugated Polymers

    Science.gov (United States)

    2016-12-26

    polymer are complementary for enhancing the absorption of the solar spectrum while their energy bands are offset structure for facilitating charge ...display a currently valid OMB control number. PLEASE DO NOT RETURN YOUR FORM TO THE ABOVE ORGANIZATION. 1. REPORT DATE (DD-MM-YYYY)      28-12-2016 2...the small molecule and the polymer are complementary for enhancing the absorption of the solar spectrum while their energy bands are offset structure

  17. Microporous conjugated polymers via homopolymerization of 2,5-diethynylthiophene

    Czech Academy of Sciences Publication Activity Database

    Bondarev, D.; Sivkova, Radoslava; Šuly, P.; Polášková, M.; Krejčí, O.; Křikavová, R.; Trávníček, Z.; Zukal, Arnošt; Kubů, Martin; Sedláček, J.

    2017-01-01

    Roč. 92, July (2017), s. 213-219 ISSN 0014-3057 R&D Projects: GA ČR(CZ) GA15-09637S Institutional support: RVO:61389013 ; RVO:61388955 Keywords : thiophene * microporous * catalysis Subject RIV: CD - Macromolecular Chemistry; CD - Macromolecular Chemistry (UFCH-W) OBOR OECD: Polymer science; Polymer science (UFCH-W) Impact factor: 3.531, year: 2016

  18. End Functionalized Nonionic Water-Dispersible Conjugated Polymers.

    Science.gov (United States)

    Zhan, Ruoyu; Liu, Bin

    2017-09-01

    2,7-Dibromofluorene monomers carrying two or four oligo(ethylene glycol) (OEG) side chains are synthesized. Heck coupling between the monomers and 1,4-divinylbenzene followed by end capping with [4-(4-bromophenoxy)butyl]carbamic acid tert-butyl ester leads to two nonionic water-dispersible poly(fluorene-alt-1,4-divinylenephenylene)s end-functionalized with amine groups after hydrolysis. In water, the polymer with a lower OEG density (P1) has poor water dispersibility with a quantum yield of 0.24, while the polymer with a higher OEG density (P2) possesses excellent water-dispersibility with a high quantum yield of 0.45. Both polymers show fluorescence enhancement and blue-shifted absorption and emission maxima in the presence of surfactant sodium dodecyl sulfate and dodecyltrimethylammonium bromide. The polymers are also resistant to ionic strength with minimal nonspecific interactions to bovine serum albumin. When biotin is incorporated into the end of the polymer backbones through N-hydroxysuccinimide/amine coupling reaction, the biotinylated polymers interact specifically with streptavidin on solid surface. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. Dye sensitized photovoltaic cells: Attaching conjugated polymers to zwitterionic ruthenium dyes

    DEFF Research Database (Denmark)

    Krebs, Frederik C; Biancardo, M.

    2006-01-01

    The synthesis of a zwitterionic ruthenium dye that binds to anatase surfaces and has a built-in functionality that allows for the attachment of a conjugated polymer chain is presented. The system was found to adsorb on the surface of anatase anchored by the ruthenium dye. Two types of devices were...... prepared: standard photoelectrochemical (PEC) solar cells and polymer solar cells. The PEC solar cells employed a sandwich geometry between TiO2 nanoporous photoanodes and Pt counter electrodes using LiI/I-2 in CH3CN as an electrolyte. The polymer solar cells employed planar anatase electrodes...

  20. Photovoltaic properties of conjugated polymer/fullerene composites on large area flexible substrates

    Directory of Open Access Journals (Sweden)

    Desta Gebeyehu

    2000-06-01

    Full Text Available In this paper we present measurements of the photovoltaic response of bulk donor-acceptor heterojunction between the conjugated polymer, poly(3-octylthiophene, P3OT, (as a donor, D and fullerene (methanofullerene, (as acceptor, A, deposited between indium tin oxide and aluminum electrodes. The innovation involves the substrate, which is a polymer foil instead of glass. These devices are based on ultrafast, reversible, metastable photoinduced electron transfer and charge separation. We also present the efficiency and stability studies on large area (6 cm x 6 cm flexible plastic solar cells with monochromatic energy conversion efficiency (e of about 1.5% and carrier collection efficiency of nearly 20%. Further more, we have investigated the surface network morphology of these films layers by atomic force microscope (AFM. The development of solar cells based on composites of organic conjugated semi-conducting polymers with fullerene derivatives can provide a new method in the exploitation of solar energy.

  1. Core/Shell Conjugated Polymer/Quantum Dot Composite Nanofibers through Orthogonal Non-Covalent Interactions

    Directory of Open Access Journals (Sweden)

    Brad W. Watson

    2016-11-01

    Full Text Available Nanostructuring organic polymers and organic/inorganic hybrid materials and controlling blend morphologies at the molecular level are the prerequisites for modern electronic devices including biological sensors, light emitting diodes, memory devices and solar cells. To achieve all-around high performance, multiple organic and inorganic entities, each designed for specific functions, are commonly incorporated into a single device. Accurate arrangement of these components is a crucial goal in order to achieve the overall synergistic effects. We describe here a facile methodology of nanostructuring conjugated polymers and inorganic quantum dots into well-ordered core/shell composite nanofibers through cooperation of several orthogonal non-covalent interactions including conjugated polymer crystallization, block copolymer self-assembly and coordination interactions. Our methods provide precise control on the spatial arrangements among the various building blocks that are otherwise incompatible with one another, and should find applications in modern organic electronic devices such as solar cells.

  2. Thermocleavable pi-Conjugated polymers. Synthesis and photovoltaic applications

    Energy Technology Data Exchange (ETDEWEB)

    Helgesen, M

    2009-10-15

    Polymer solar cells (plastic solar cells) have seen remarkable improvements in recent years where power conversion efficiencies of up to 6% have been reported for small area devices. However in terms of stability polymer solar cells degrade during illumination and in the dark leading to operational lifetimes that are generally very poor. There has been a recent interest in the operational stability of devices and more importantly on the understanding of why devices and materials break down. This has lead to the discovery of a new class of materials that enable exceptionally long device lifetimes (>20000 hours). This Ph.D. thesis describes the synthesis, characterization and photovoltaic applications of these novel polymer materials. A key feature of these materials is that solubilizing thermocleavable alkyl ester side chains are introduced on the polymer backbone. The side chains make the polymer soluble in organic solvents and allow film formation via solution processing. Subsequently they can be removed by heating in a post-processing step forming a harder insoluble material with enhanced stability. These new thermocleavable materials can potentially offer higher chromophore density, higher level processing and improved stability in a solar cell device. Methods are developed for the incorporation of alkoxy chains and thermocleavable ester groups on the benzothiadiazole and the thiophene units in an attempt to evolve the PDTBT system to a more advanced level. The synthesis and photovoltaic applications of the PDTTP and PDTBT systems is described. (author)

  3. Electroluminescence of Multicomponent Conjugated Polymers. 1. Roles of Polymer/Polymer Interfaces in Emission Enhancement and Voltage-Tunable Multicolor Emission in Semiconducting Polymer/Polymer Heterojunctions

    National Research Council Canada - National Science Library

    Zhang, Xuejun, Ph.D

    1999-01-01

    Effects of the electronic structure of polymer/polymer interfaces on the electroluminescence efficiency and tunable multicolor emission of polymer heterojunction light-emitting diodes were explored...

  4. Synthesis, characterization and comparison of polythiophene ...

    Indian Academy of Sciences (India)

    38

    Synthesis, characterization and comparison of polythiophene-carbon ... b Nanotechnology Research Institute, School of Chemical Engineering, Babol University of Technology, Babol, ..... The scan range was from −0.24 to 1.2 V in reference to.

  5. Modelling the effect of nonplanarity on charge transport along conjugated polymer chains

    International Nuclear Information System (INIS)

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

    2007-01-01

    Conjugated polymers show interesting properties that make them appropriated for nanoelectronics. Several studies of poly(p-phenylene vinylene) (PPV) have suggested that each polymer chain consists of several planar segments, with conjugation length of nanoscale dimension, linked by twists or kinks. A pronounced twist between two planar segments in a PPV chain not only causes loss of main-chain conjugation but it may also alter electron and hole mobility along the chain, which has further implications for the percolation of charge through the polymer film. We used self-consistent quantum molecular dynamics calculations to provide information on the electric field needed to move the injected charges (either electrons or holes) along the planar segments of PPV and to cross the twist between two planar segments perpendicular to each other. Field-dependent charge mobility was also estimated for conjugated segments of various lengths. Our results suggest that electrons can cross the twist between adjacent planar segments for lower applied electric fields than holes if there is no more than one electronic charge (electron or hole) on the PPV chain, otherwise similar fields are needed

  6. Photoluminescence quenching through resonant energy transfer in blends of conjugated polymer with low-molecular acceptor

    International Nuclear Information System (INIS)

    Zapunidi, S. A.; Paraschuk, D. Yu.

    2008-01-01

    A model is proposed for photoluminescence quenching due to resonant energy transfer in a blend of a conjugated polymer and a low-molecular energy acceptor. An analytical dependence of the normalized photoluminescence intensity on the acceptor concentration is derived for the case of a homogeneous blend. This dependence can be described by two fitting parameters related to the Foerster radii for energy transfer between conjugated segments of the polymer and between the conjugated polymer segment and the energy acceptor. Asymptotic approximations are obtained for the model dependence that make it possible to estimate the contribution from the spatial migration of excitons to the photoluminescence quenching. The proposed model is used to analyze experimental data on the photoluminescence quenching in a blend of the soluble derivative of poly(p-phenylene vinylene) and trinitrofluorenone [13]. The Foerster radius for resonant energy transfer between the characteristic conjugated segment of poly(p-phenylene vinylene) and the energy acceptor is determined to be r F = 2.6 ± 0.3 nm

  7. Photoinduced reversible switching of charge carrier mobility in conjugated polymers

    Czech Academy of Sciences Publication Activity Database

    Weiter, M.; Navrátil, J.; Vala, M.; Toman, Petr

    2009-01-01

    Roč. 48, č. 1 (2009), 10401_1-10401_6 ISSN 1286-0042 R&D Projects: GA ČR GA203/06/0285; GA AV ČR KAN401770651 Institutional research plan: CEZ:AV0Z40500505 Keywords : polymers * switch * charge carrier mobility Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 0.756, year: 2009

  8. Photovoltaic properties of conjugated polymer/fullerene composites ...

    African Journals Online (AJOL)

    The innovation involves the substrate, which is a polymer foil instead of glass. These devices are based on ultrafast, reversible, metastable photoinduced electron transfer and charge separation. We also present the efficiency and stability studies on large area (6 cm x 6 cm) flexible plastic solar cells with monochromatic ...

  9. Incorporating functionalized polyethylene glycol lipids into reprecipitated conjugated polymer nanoparticles for bioconjugation and targeted labeling of cells

    Science.gov (United States)

    Kandel, Prakash K.; Fernando, Lawrence P.; Ackroyd, P. Christine; Christensen, Kenneth A.

    2011-03-01

    We report a simple and rapid method to prepare extremely bright, functionalized, stable, and biocompatible conjugated polymer nanoparticles incorporating functionalized polyethylene glycol (PEG) lipids by reprecipitation. These nanoparticles retain the fundamental spectroscopic properties of conjugated polymer nanoparticles prepared without PEG lipid, but demonstrate greater hydrophilicity and quantum yield compared to unmodified conjugated polymer nanoparticles. The sizes of these nanoparticles, as determined by TEM, were 21-26 nm. Notably, these nanoparticles were prepared with several PEG lipid functional end groups, including biotin and carboxy moieties that can be easily conjugated to biomolecules. We have demonstrated the availability of these end groups for functionalization using the interaction of biotin PEG lipid conjugated polymer nanoparticles with streptavidin. Biotinylated PEG lipid conjugated polymer nanoparticles bound streptavidin-linked magnetic beads, while carboxy and methoxy PEG lipid modified nanoparticles did not. Similarly, biotinylated PEG lipid conjugated polymer nanoparticles bound streptavidin-coated glass slides and could be visualized as diffraction-limited spots, while nanoparticles without PEG lipid or with non-biotin PEG lipid end groups were not bound. To demonstrate that nanoparticle functionalization could be used for targeted labelling of specific cellular proteins, biotinylated PEG lipid conjugated polymer nanoparticles were bound to biotinylated anti-CD16/32 antibodies on J774A.1 cell surface receptors, using streptavidin as a linker. This work represents the first demonstration of targeted delivery of conjugated polymer nanoparticles and demonstrates the utility of these new nanoparticles for fluorescence based imaging and sensing.We report a simple and rapid method to prepare extremely bright, functionalized, stable, and biocompatible conjugated polymer nanoparticles incorporating functionalized polyethylene glycol (PEG

  10. Bipolar and Unipolar Silylene-Diphenylene σ-π Conjugated Polymer Route for Highly Efficient Electrophosphorescence

    Science.gov (United States)

    Chang, Yao-Tang; Sharma, Sunil; Hung, Miao-Ken; Lee, Yu-Hsuan; Chen, Show-An

    2016-12-01

    σ-π conjugated polymer strategy is proposed for designing electroluminescent host polymers with silylene-diphenylene as the backbone repeat unit giving a high triplet energy (ET = 2.67 eV). By incorporation of high ET (3.0 eV) electron (oxadiazole, OXD) and hole (triphenyl amine, TPA) transport moieties, or TPA alone (in this case, the main chain acts as electron transport channel) as side arms on the silylene, the high ET bipolar and unipolar polymers are formed, allowing a use of iridium green phosphor (Ir(ppy)2(acac), Ir-G) (ET = 2.40 eV) as the dopant. The matching of energy levels of the dopant with the hosts, leading to charge trapping into it; and singlets and triplets of the exciplex and excimer can be harvested via energy transfer to the dopant. Using these host-guest systems as the emitting layer, chlorinated indium-tin-oxide (Cl-ITO) as the anode, and benzimidazole derivative (TPBI) as the electron transport layer, this two-layer device gives the high luminance efficiency 80.1 cd/A and external quantum efficiency 21.2%, which is the best among the report values for polymer light emitting diode (PLED) in the literatures. This example manifests that σ-π conjugated polymer strategy is a promising route for designing polymer host for efficient electrophosphorescence.

  11. Amplified spontaneous emission from the exciplex state of a conjugated polymer "PFO" in oleic acid

    Science.gov (United States)

    Idriss, Hajo; Taha, Kamal K.; Aldaghri, O.; Alhathlool, R.; AlSalhi, M. S.; Ibnaouf, K. H.

    2016-09-01

    The amplified spontaneous emission (ASE) characteristics of a conjugated polymer poly (9, 9-dioctylfluorenyl-2, 7-diyl) (PFO) in oleic acid have been studied under different concentrations and temperatures. Here, the ASE spectra of PFO in oleic acid have been obtained using a transverse cavity configuration where the conjugated PFO was pumped by laser pulses from the third harmonic of Nd: YAG laser (355 nm). The PFO in oleic acid produces ASE from an exciplex state - a new molecular species. The obtained results were compared with the PFO in benzene. Such ASE spectra from the exciplex state have not been observed for the PFO in benzene.

  12. Conjugated polymer energy level shifts in lithium-ion battery electrolytes.

    Science.gov (United States)

    Song, Charles Kiseok; Eckstein, Brian J; Tam, Teck Lip Dexter; Trahey, Lynn; Marks, Tobin J

    2014-11-12

    The ionization potentials (IPs) and electron affinities (EAs) of widely used conjugated polymers are evaluated by cyclic voltammetry (CV) in conventional electrochemical and lithium-ion battery media, and also by ultraviolet photoelectron spectroscopy (UPS) in vacuo. By comparing the data obtained in the different systems, it is found that the IPs of the conjugated polymer films determined by conventional CV (IPC) can be correlated with UPS-measured HOMO energy levels (EH,UPS) by the relationship EH,UPS = (1.14 ± 0.23) × qIPC + (4.62 ± 0.10) eV, where q is the electron charge. It is also found that the EAs of the conjugated polymer films measured via CV in conventional (EAC) and Li(+) battery (EAB) media can be linearly correlated by the relationship EAB = (1.07 ± 0.13) × EAC + (2.84 ± 0.22) V. The slopes and intercepts of these equations can be correlated with the dielectric constants of the polymer film environments and the redox potentials of the reference electrodes, as modified by the surrounding electrolyte, respectively.

  13. Synthesis of conjugated polymers with complex architecture for photovoltaic applications

    DEFF Research Database (Denmark)

    Kiriy, Anton; Krebs, Frederik C

    2017-01-01

    A common approach to bulk heterojunction solar cells involves a “trialand- error” approach in finding optimal kinetically unstable morphologies. An alternative approach assumes the utilization of complex polymer architectures, such as donor–acceptor block copolymers. Because of a covalent preorga...... preorganization of the donor and acceptor components, these materials may form desirable morphologies at thermodynamic equilibrium. This chapter reviews synthetic approaches to such architectures and shows the first photovoltaic results....

  14. HYDROGELS BASED ON POLYMERS OF DEXTRAN TYRAMINE AND TYRAMINE CONJUGATES OF NATURAL POLYMERS

    NARCIS (Netherlands)

    Feijen, Jan; Karperien, Marcel; Jin, R.; Moreira Teixeira, Liliana; Dijkstra, Pieter J.

    2012-01-01

    The invention relates to composition comprising a dextran-tyramine conjugate and a conjugate selected from the group consisting of chondroitin sulphate-tyramine, collagen-tyramine, chitosan-tyramine, chitosan-phloretic acid, gelatine-tyramine, heparan sulphate-tyramine, keratin sulphate-tyramine,

  15. HYDROGELS BASED ON POLYMERS OF DEXTRAN TYRAMINE AND TYRAMINE CONJUGATES OF NATURAL POLYMERS

    NARCIS (Netherlands)

    Karperien, H.B.J.; Jin, R.; Moreira Teixeira, Liliana; Feijen, Jan; Dijkstra, Pieter J.

    2011-01-01

    The invention relates to composition comprising a dextran-tyramine conjugate and a conjugate selected from the group consisting of chondroitin sulphate-tyramine, collagen-tyramine, chitosan-tyramine, chitosan-phloretic acid, gelatine-tyramine, heparan sulphate-tyramine, keratin sulphate tyramine,

  16. Structure-processing-property correlations in thin films of conjugated polymer nanocomposites and blends

    Science.gov (United States)

    Sreeram, Arvind

    Conjugated polymers have found several applications in recent years, in energy conversion and storage devices such as organic light emitting diodes, solar cells, batteries, and super capacitors. Thin films of polymers used for these applications need to be mechanically and thermally stable to withstand the harsh operating conditions. Although there is significant information on the optoelectronic properties of many of these polymers, there are only few studies on their mechanical properties. There is little information in the literature on how processing of these films influence mechanical properties. In the first part of this study, poly(p-phenylene vinylene) (PPV) films were prepared by thermolytic conversion of poly[p -phenylene (tetrahydrothiophenium)ethylene chloride] precursor films, at different temperatures and the kinetics of reaction was investigated using thermogravimetry and Fourier transform infrared (FTIR) spectroscopy. The mechanical properties of the films, studied using nanoindentation, showed a dependence on the extent of conversion and chemical composition of the films. The presence of chemical defects (e.g., carbonyl groups, detected using FTIR spectroscopy), was also found to have a noticeable effect on the modulus and hardness of the films. The storage modulus, E', and plasticity decreased with an increase in conversion, whereas the loss modulus, E", showed the opposite trend. Both the precursor and the fully-converted PPV films were found to have significantly lower E" than E', consistent with the glassy nature of the polymers at room temperature. In the second part of the study, polyacetylene films were synthesized by acid-catalyzed dehydration reaction of poly(vinyl alcohol) (PVA) precursor films. The kinetics of this reaction was monitored by thermogravimetry. The chemical structure of the conjugated polymer films was characterized by Raman and IR spectroscopy. Polyacetylene films incorporated with 1-propyl-3-methylimidazolium ionic liquid

  17. Fine-tuning of electronic properties in donor-acceptor conjugated polymers based on oligothiophenes

    Science.gov (United States)

    Imae, Ichiro; Sagawa, Hitoshi; Harima, Yutaka

    2018-03-01

    A novel series of donor-acceptor conjugated polymers having oligothiophenes with well-defined structures were synthesized and their optical, electrochemical, and photovoltaic properties were investigated. It was found that the absorption bands of polymers were red-shifted with increasing number of ethylenedioxy groups added to each oligothiophene unit and that their band edges reached over 1000 nm. The systematical fine-tuning of the electronic properties was achieved using the chemical structures of oligothiophene units. Photovoltaic cells based on polymer/(6,6)-phenyl C61 butyric acid methyl ester (PC61BM) exhibited power conversion efficiencies in the range from 0.004 to 1.10%, reflecting the electronic properties of the polymers.

  18. Ambipolar Organic Phototransistors with p-Type/n-Type Conjugated Polymer Bulk Heterojunction Light-Sensing Layers

    KAUST Repository

    Nam, Sungho; Han, Hyemi; Seo, Jooyeok; Song, Myeonghun; Kim, Hwajeong; Anthopoulos, Thomas D.; McCulloch, Iain; Bradley, Donal D C; Kim, Youngkyoo

    2016-01-01

    Ambipolar organic phototransistors with sensing channel layers, featuring p-type and n-type conjugated polymer bulk heterojunctions, exhibit outstanding light-sensing characteristics in both p-channel and n-channel sensing operation modes.

  19. Solvent-dependent self-assembly and ordering in slow-drying semi-crystalline conjugated polymer solutions

    KAUST Repository

    Zhao, Kui; Yu, Xinhong; Li, Ruipeng; Amassian, Aram; Han, Yanchun

    2015-01-01

    The mechanistic understanding of the intrinsic molecular self-assembly of conjugated polymers is of immense importance to controlling the microstructure development in organic semiconducting thin films, with meaningful impact on charge transport

  20. Ambipolar Organic Phototransistors with p-Type/n-Type Conjugated Polymer Bulk Heterojunction Light-Sensing Layers

    KAUST Repository

    Nam, Sungho

    2016-11-18

    Ambipolar organic phototransistors with sensing channel layers, featuring p-type and n-type conjugated polymer bulk heterojunctions, exhibit outstanding light-sensing characteristics in both p-channel and n-channel sensing operation modes.

  1. Inhibitor-decorated Polymer Conjugates Targeting Fibroblast Activation Protein

    Czech Academy of Sciences Publication Activity Database

    Dvořáková, Petra; Bušek, P.; Knedlík, Tomáš; Schimer, Jiří; Etrych, Tomáš; Kostka, Libor; Stollinová Šromová, L.; Šubr, Vladimír; Šácha, Pavel; Šedo, A.; Konvalinka, Jan

    2017-01-01

    Roč. 60, č. 20 (2017), s. 8385-8393 ISSN 0022-2623 R&D Projects: GA MZd(CZ) NV15-31379A; GA MŠk(CZ) LM2015064; GA MŠk LO1302 Institutional support: RVO:61388963 ; RVO:61389013 Keywords : dipeptidyl peptidase IV * metastatic colorectal cancer * integral membrane protease Subject RIV: CE - Biochemistry; CD - Macromolecular Chemistry (UMCH-V) OBOR OECD: Biochemistry and molecular biology; Polymer science (UMCH-V) Impact factor: 6.259, year: 2016

  2. Influence of Molecular Conformations and Microstructure on the Optoelectronic Properties of Conjugated Polymers

    Directory of Open Access Journals (Sweden)

    Ioan Botiz

    2014-03-01

    Full Text Available It is increasingly obvious that the molecular conformations and the long-range arrangement that conjugated polymers can adopt under various experimental conditions in bulk, solutions or thin films, significantly impact their resulting optoelectronic properties. As a consequence, the functionalities and efficiencies of resulting organic devices, such as field-effect transistors, light-emitting diodes, or photovoltaic cells, also dramatically change due to the close structure/property relationship. A range of structure/optoelectronic properties relationships have been investigated over the last few years using various experimental and theoretical methods, and, further, interesting correlations are continuously revealed by the scientific community. In this review, we discuss the latest findings related to the structure/optoelectronic properties interrelationships that exist in organic devices fabricated with conjugated polymers in terms of charge mobility, absorption, photoluminescence, as well as photovoltaic properties.

  3. Influence of Molecular Conformations and Microstructure on the Optoelectronic Properties of Conjugated Polymers

    KAUST Repository

    Botiz, Ioan; Stingelin, Natalie

    2014-01-01

    It is increasingly obvious that the molecular conformations and the long-range arrangement that conjugated polymers can adopt under various experimental conditions in bulk, solutions or thin films, significantly impact their resulting optoelectronic properties. As a consequence, the functionalities and efficiencies of resulting organic devices, such as field-effect transistors, light-emitting diodes, or photovoltaic cells, also dramatically change due to the close structure/property relationship. A range of structure/optoelectronic properties relationships have been investigated over the last few years using various experimental and theoretical methods, and, further, interesting correlations are continuously revealed by the scientific community. In this review, we discuss the latest findings related to the structure/optoelectronic properties interrelationships that exist in organic devices fabricated with conjugated polymers in terms of charge mobility, absorption, photoluminescence, as well as photovoltaic properties. © 2014 by the authors.

  4. Particle-in-a-box model of one-dimensional excitons in conjugated polymers

    Science.gov (United States)

    Pedersen, Thomas G.; Johansen, Per M.; Pedersen, Henrik C.

    2000-04-01

    A simple two-particle model of excitons in conjugated polymers is proposed as an alternative to usual highly computationally demanding quantum chemical methods. In the two-particle model, the exciton is described as an electron-hole pair interacting via Coulomb forces and confined to the polymer backbone by rigid walls. Furthermore, by integrating out the transverse part, the two-particle equation is reduced to one-dimensional form. It is demonstrated how essentially exact solutions are obtained in the cases of short and long conjugation length, respectively. From a linear combination of these cases an approximate solution for the general case is obtained. As an application of the model the influence of a static electric field on the electron-hole overlap integral and exciton energy is considered.

  5. Influence of Molecular Conformations and Microstructure on the Optoelectronic Properties of Conjugated Polymers

    KAUST Repository

    Botiz, Ioan

    2014-03-19

    It is increasingly obvious that the molecular conformations and the long-range arrangement that conjugated polymers can adopt under various experimental conditions in bulk, solutions or thin films, significantly impact their resulting optoelectronic properties. As a consequence, the functionalities and efficiencies of resulting organic devices, such as field-effect transistors, light-emitting diodes, or photovoltaic cells, also dramatically change due to the close structure/property relationship. A range of structure/optoelectronic properties relationships have been investigated over the last few years using various experimental and theoretical methods, and, further, interesting correlations are continuously revealed by the scientific community. In this review, we discuss the latest findings related to the structure/optoelectronic properties interrelationships that exist in organic devices fabricated with conjugated polymers in terms of charge mobility, absorption, photoluminescence, as well as photovoltaic properties. © 2014 by the authors.

  6. Charge carrier motion in disordered conjugated polymers: a multiscale ab-initio study

    Energy Technology Data Exchange (ETDEWEB)

    Vukmirovic, Nenad; Wang, Lin-Wang

    2009-11-10

    We developed an ab-initio multiscale method for simulation of carrier transport in large disordered systems, based on direct calculation of electronic states and electron-phonon coupling constants. It enabled us to obtain the never seen before rich microscopic details of carrier motion in conjugated polymers, which led us to question several assumptions of phenomenological models, widely used in such systems. The macroscopic mobility of disordered poly(3- hexylthiophene) (P3HT) polymer, extracted from our simulation, is in agreement with experimental results from the literature.

  7. Effects of alkyl chain positioning on conjugated polymer microstructure and field-effect mobilities

    KAUST Repository

    Schroeder, Bob C.

    2015-07-02

    Solubilizing alkyl chains play a crucial role in the design of semiconducting polymers because they define the materials solubility and processability as well as both the crystallinity and solid-state microstructure. In this paper, we present a scarcely explored design approach by attaching the alkyl side chains on one side (cis-) or on both sides (trans-) of the conjugated backbone. We further investigate the effects of this structural modification on the solid-state properties of the polymers and on the charge-carrier mobilities in organic thin-film transistors. Copyright © Materials Research Society 2015

  8. Effects of alkyl chain positioning on conjugated polymer microstructure and field-effect mobilities

    KAUST Repository

    Schroeder, Bob C.; Nielsen, Christian B.; Westacott, Paul; Smith, Jeremy; Rossbauer, Stephan; Anthopoulos, Thomas D.; Stingelin, Natalie; McCulloch, Iain

    2015-01-01

    Solubilizing alkyl chains play a crucial role in the design of semiconducting polymers because they define the materials solubility and processability as well as both the crystallinity and solid-state microstructure. In this paper, we present a scarcely explored design approach by attaching the alkyl side chains on one side (cis-) or on both sides (trans-) of the conjugated backbone. We further investigate the effects of this structural modification on the solid-state properties of the polymers and on the charge-carrier mobilities in organic thin-film transistors. Copyright © Materials Research Society 2015

  9. Synthesis of Donor-Acceptor Conjugated Polymers by "CLICK" Polymerization for OPV applications

    DEFF Research Database (Denmark)

    Brandt, Rasmus Guldbæk; Yu, Donghong

    The intent of this study was to utilize the Copper(I)-catalyzed Azide Alkyne Cycloaddition (CuAAC) as a polymerization technique (“Click” Polymerization) for synthesizing novel π-conjugated low band gap polymers for organic photovoltaic applications (OPV). The chosen approach was to synthesize...... an alternating electron donating (donor, D) and electron withdrawing (acceptor, A) co-polymer. The chosen monomers were well known units, and the novelty lies in using the monomer units with the click methodology. An insoluble alternating copolymer consisting of 2,7-diazido-9,9-dioctyl-9Hflourene and 1...

  10. A possibility for generation of two species of charge carriers along main-chain and side-chains for a π-conjugated polymer

    International Nuclear Information System (INIS)

    Kudo, Yuki; Kawabata, Kohsuke; Goto, Hiromasa

    2013-01-01

    Iodide doping produces charge carriers in π-conjugated polymers. Solitons can be generated in the case of polyacetylene, and polarons in the case of aromatic-type conjugated polymers. We synthesized a conjugated main-chain/side-chain polymer, which consists of polyene in the main-chain and aromatic-type conjugated units in the side-chains. Based on the SSH (Su, Schrieffer, Heeger) theoretical model of solitons in one-dimensional conjugated polymers, we experimentally carried out chemical doping to the main-chain/side-chains conjugated polymer. Generation of the charge carriers was examined by electron spin resonance spectroscopy. This study may lead to realization of a dual doping system of solitons and polarons in π-conjugation expanded to two-dimensional directions in polymers.

  11. A New Property of Conjugated Polymer PFP: Catalytic Degradation of Methylene Blue Aqueous Solution

    Institute of Scientific and Technical Information of China (English)

    2005-01-01

    A new property of conjugated polymer poly(furancarbinol-co-phenol)(PFP) was studied.The target copolymer was used as a catalyst after proper heating treatment. And dye methylene blue (MB) could be fully degraded and largely mineralized on PFP, under natural light or even in dark, in a few minutes. Furthermore, the catalytic activity could be preserved after several runs and the catalyst was readily separated. The effect of calcination temperature was also observed.

  12. Design of porphyrin-based conjugated microporous polymers with enhanced singlet oxygen productivity

    Czech Academy of Sciences Publication Activity Database

    Hynek, Jan; Rathouský, Jiří; Demel, Jan; Lang, Kamil

    2016-01-01

    Roč. 6, č. 50 (2016), s. 44279-44287 ISSN 2046-2069 R&D Projects: GA ČR(CZ) GA16-15020S Institutional support: RVO:61388980 ; RVO:61388955 Keywords : Conjugated microporous polymers * Crystalline materials * Metal organic framework * biomimetic catalysis Subject RIV: CA - Inorganic Chemistry; CF - Physical ; Theoretical Chemistry (UFCH-W) Impact factor: 3.108, year: 2016

  13. Synthesis of metalloporphyrin-based conjugated microporous polymer spheres directed by bipyridine-type ligands.

    Science.gov (United States)

    Ji, Guipeng; Yang, Zhenzhen; Zhao, Yanfei; Zhang, Hongye; Yu, Bo; Xu, Jilei; Xu, Huanjun; Liu, Zhimin

    2015-04-30

    Zinc porphyrin (TP-Zn)-based conjugated microporous polymer (Zn-CMP) spheres were obtained via Sonagashira-Hagihara cross coupling reactions between 5,10,15,20-tetrakis(4-ethynylphenyl)porphyrin-Zn(II) and brominated monomers directed by bidentate bipyridine (BP)-type ligands for the first time, and the sphere diameters could be adjusted from 320 to 740 nm. The coordination between BP and TP-Zn was proved to be the key to forming spheres.

  14. HPMA copolymer-based polymer conjugates for the delivery and controlled release of retinoids

    Czech Academy of Sciences Publication Activity Database

    Lidický, Ondřej; Šírová, Milada; Etrych, Tomáš

    2016-01-01

    Roč. 65, Suppl. 2 (2016), S233-S241 ISSN 0862-8408 R&D Projects: GA MŠk(CZ) LQ1604 Institutional support: RVO:61389013 ; RVO:61388971 Keywords : polymer conjugate * retinoid * HPMA Subject RIV: EB - Genetics ; Molecular Biology; EA - Cell Biology (MBU-M) Impact factor: 1.461, year: 2016 http://www.biomed.cas.cz/physiolres/pdf/65%20Suppl%202/65_S233.pdf

  15. Star polymer-drug conjugates with pH-controlled drug release and carrier degradation

    Czech Academy of Sciences Publication Activity Database

    Kostková, Hana; Schindler, Lucie; Kotrchová, Lenka; Kovář, Marek; Šírová, Milada; Kostka, Libor; Etrych, Tomáš

    2017-01-01

    Roč. 2017, 3 January (2017), s. 1-10, č. článku 8675435. ISSN 1687-4110 R&D Projects: GA MŠk(CZ) LQ1604 Institutional support: RVO:61389013 ; RVO:61388971 Keywords : star conjugate * HPMA copolymer * doxorubicin Subject RIV: CD - Macromolecular Chemistry; EE - Microbiology, Virology (MBU-M) OBOR OECD: Polymer science; Microbiology (MBU-M) Impact factor: 1.871, year: 2016

  16. α-Methylprednisolone conjugated cyclodextrin polymer-based nanoparticles for rheumatoid arthritis therapy

    Directory of Open Access Journals (Sweden)

    Jungyeon Hwang

    2008-10-01

    Full Text Available Jungyeon Hwang1, Kathleen Rodgers2, James C Oliver3, Thomas Schluep11Insert Therapeutics, Inc., Pasadena, CA, USA; 2Livingston Research Institute, Los Angeles, CA, USA; James C Oliver, Peptagen, Inc., Raleigh, NC USAAbstract: A glycinate derivative of α-methylprednisolone (MP was prepared and conjugated to a linear cyclodextrin polymer (CDP with a loading of 12.4% w/w. The polymer conjugate (CDP-MP self-assembled into nanoparticles with a size of 27 nm. Release kinetics of MP from the polymer conjugate showed a half-life (t1/2 of 50 h in phosphate buffer solution (PBS and 19 h in human plasma. In vitro, the proliferation of human lymphocytes was suppressed to a similar extent but with a delayed effect when CDP-MP was compared with free MP. In vivo, CDP-MP was administered intravenously to mice with collagen-induced arthritis and compared with free MP. CDP-MP was administered weekly for six weeks (0.07, 0.7, and 7 mg/kg/week and MP was administered daily for six weeks (0.01, 0.1, and 1 mg/kg/day. Body weight changes were minimal in all animals. After 28 days, a significant decrease in arthritis score was observed in animals treated weekly with an intermediate or high dose of CDP-MP. Additionally, dorsoplantar swelling was reduced to baseline in animals treated with CDP-MP at the intermediate and high dose level. Histological evaluation showed a reduction in synovitis, pannus formation and disruption of architecture at the highest dose level of CDP-MP. MP administered daily at equivalent cumulative doses showed minimal efficacy in this model. This study demonstrates that conjugation of MP to a cyclodextrin-polymer may improve its efficacy, leading to lower doses and less frequent administration for a safer and more convenient management of rheumatoid arthritis.Keywords: α-methylprednisolone (MP, cyclodextrin polymer (CDP, polymer conjugate (CDP-MP, rheumatoid arthritis (RA, enhanced permeability and retention effect (EPR

  17. Synthesis and characterization of a cysteine xyloglucan conjugate as mucoadhesive polymer

    Directory of Open Access Journals (Sweden)

    Mangesh Bhalekar

    2013-06-01

    Full Text Available The aim of this study was to improve the mucoadhesive potential of xyloglucan polymer by the covalent attachment of cysteine as thiol moiety. The parent polymer xyloglucan was chemically modified by introducing sulphydryl bearing compound L-cysteine HCl. Different batches of xyloglucan-cysteine conjugates were prepared at varying reaction pH (2-6 and evaluated for optimum thiol incorporation, disulphide group content, swelling behavior, rheological properties and mucoadhesive properties. The obtained conjugates characterized in vitro by quantification of immobilized thiol groups; showed maximum thiol incorporation on xyloglucan (7.67 ± 0.14 % at pH 5. The disulphide group content was found maximum (2.83 ± 0.12 at pH 6. The water uptake at end of 4 h was 5.0 for xyloglucan and was found to decrease in thiolated derivatives with increase in thiolation. Mucoadhesion studies revealed that mucoadhesion of xyloglucan-cysteine conjugate increased more than twice compared to the unmodified polymer. The viscosity of thiomer was more than that of xyloglucan because of formation of disulphide bonds.

  18. Synthesis and Characterisation of Biocompatible Polymer-Conjugated Magnetic Beads for Enhancement Stability of Urease.

    Science.gov (United States)

    Doğaç, Yasemin Ispirli; Teke, Mustafa

    2016-04-01

    We reported natural polymer-conjugated magnetic featured urease systems for removal of urea effectively. The optimum temperature (20-60 °C), optimum pH (3.0-10.0), kinetic parameters, thermal stability (4-70 °C), pH stability (4.0-9.0), operational stability (0-250 min), reusability (18 times) and storage stability (24 weeks) were studied for characterisation of the urease-encapsulated biocompatible polymer-conjugated magnetic beads. Also, the surface groups and chemical structure of the magnetic beads were determined by using attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR). The all urease-encapsulated magnetic beads protected their stability of 30-45 % relative activity at 70 °C. A significant increase was observed at their pH stability compared with the free urease for both acidic and alkaline medium. Besides this, their repeatability activity were approximately 100 % during 4(th) run. They showed residual activity of 50 % after 16 weeks. The importance of this work is enhancement stability of immobilised urease by biocompatible polymer-conjugated magnetic beads for the industrial application based on removal of urea.

  19. Peptides, proteins and peptide/protein-polymer conjugates as drug delivery system.

    Science.gov (United States)

    Mukherjee, Biswajit; Karmakar, Swapna D; Hossain, Chowdhury M; Bhattacharya, Sanchari

    2014-01-01

    In the last few decades, novel drug delivery strategies have been a big priority to the formulation scientists. Peptides and proteins have drawn a special attention for their wide scope in the area. Serum albumin, transferrin, recom- binant proteins, virus capsids etc. are used as carrier for drug and biomolecules. Conjugates of polymers with proteins have also shown strong potency in the field of drug delivery. Polyethylene glycol is one of the most successful polymers that has been used extensively to develop protein conjugated formulations. Besides, polyvinyl pyrrolidone, polylactic-co- glycolic acid, N-(2-hydroxypropyl) methacrylamide copolymer, polyglutamic acid have also been investigated. In this re- view, we will highlight on the most recent overview of various advantages, limitations and marketed products of proteins, peptides and protein/peptide-polymer conjugates as drug carriers, such products in clinical trials and their various uses in the field of modern drug delivery. Understanding the key features of these materials and the vigorous research in this field will develop new drug formulations that will combat various types of life-threatening diseases.

  20. Influence of the side chain and substrate on polythiophene thin film surface, bulk, and buried interfacial structures.

    Science.gov (United States)

    Xiao, Minyu; Jasensky, Joshua; Zhang, Xiaoxian; Li, Yaoxin; Pichan, Cayla; Lu, Xiaolin; Chen, Zhan

    2016-08-10

    The molecular structures of organic semiconducting thin films mediate the performance of various devices composed of such materials. To fully understand how the structures of organic semiconductors alter on substrates due to different polymer side chains and different interfacial interactions, thin films of two kinds of polythiophene derivatives with different side-chains, poly(3-hexylthiophene) (P3HT) and poly(3-potassium-6-hexanoate thiophene) (P3KHT), were deposited and compared on various surfaces. A combination of analytical tools was applied in this research: contact angle goniometry and X-ray photoelectron spectroscopy (XPS) were used to characterize substrate dielectric surfaces with varied hydrophobicity for polymer film deposition; X-ray diffraction and UV-vis spectroscopy were used to examine the polythiophene film bulk structure; sum frequency generation (SFG) vibrational spectroscopy was utilized to probe the molecular structures of polymer film surfaces in air and buried solid/solid interfaces. Both side-chain hydrophobicity and substrate hydrophobicity were found to mediate the crystallinity of the polythiophene film, as well as the orientation of the thiophene ring within the polymer backbone at the buried polymer/substrate interface and the polymer thin film surface in air. For the same type of polythiophene film deposited on different substrates, a more hydrophobic substrate surface induced thiophene ring alignment with the surface normal at both the buried interface and on the surface in air. For different films (P3HT vs. P3KHT) deposited on the same dielectric substrate, a more hydrophobic polythiophene side chain caused the thiophene ring to align more towards the surface at the buried polymer/substrate interface and on the surface in air. We believe that the polythiophene surface, bulk, and buried interfacial molecular structures all influence the hole mobility within the polythiophene film. Successful characterization of an organic conducting

  1. Naphthalene Diimide Based n-Type Conjugated Polymers as Efficient Cathode Interfacial Materials for Polymer and Perovskite Solar Cells.

    Science.gov (United States)

    Jia, Tao; Sun, Chen; Xu, Rongguo; Chen, Zhiming; Yin, Qingwu; Jin, Yaocheng; Yip, Hin-Lap; Huang, Fei; Cao, Yong

    2017-10-18

    A series of naphthalene diimide (NDI) based n-type conjugated polymers with amino-functionalized side groups and backbones were synthesized and used as cathode interlayers (CILs) in polymer and perovskite solar cells. Because of controllable amine side groups, all the resulting polymers exhibited distinct electronic properties such as oxidation potential of side chains, charge carrier mobilities, self-doping behaviors, and interfacial dipoles. The influences of the chemical variation of amine groups on the cathode interfacial effects were further investigated in both polymer and perovskite solar cells. We found that the decreased electron-donating property and enhanced steric hindrance of amine side groups substantially weaken the capacities of altering the work function of the cathode and trap passivation of the perovskite film, which induced ineffective interfacial modifications and declining device performance. Moreover, with further improvement of the backbone design through the incorporation of a rigid acetylene spacer, the resulting polymers substantially exhibited an enhanced electron-transporting property. Upon use as CILs, high power conversion efficiencies (PCEs) of 10.1% and 15.2% were, respectively, achieved in polymer and perovskite solar cells. Importantly, these newly developed n-type polymers were allowed to be processed over a broad thickness range of CILs in photovoltaic devices, and a prominent PCE of over 8% for polymer solar cells and 13.5% for perovskite solar cells can be achieved with the thick interlayers over 100 nm, which is beneficial for roll-to-roll coating processes. Our findings contribute toward a better understanding of the structure-performance relationship between CIL material design and solar cell performance, and provide important insights and guidelines for the design of high-performance n-type CIL materials for organic and perovskite optoelectronic devices.

  2. The Curious Case of Fluorination of Conjugated Polymers for Solar Cells.

    Science.gov (United States)

    Zhang, Qianqian; Kelly, Mary Allison; Bauer, Nicole; You, Wei

    2017-09-19

    Organic solar cells (OSCs) have been a rising star in the field of renewable energy since the introduction of the bulk heterojunction (BHJ) in 1992. Recent advances have pushed the efficiencies of OSCs to over 13%, an impressive accomplishment via collaborative efforts in rational materials design and synthesis, careful device engineering, and fundamental understanding of device physics. Throughout these endeavors, several design principles for the conjugated donor polymers used in such solar cells have emerged, including optimizing the conjugated backbone with judicious selection of building blocks, side-chain engineering, and substituents. Among all of the substituents, fluorine is probably the most popular one; improved device characteristics with fluorination have frequently been reported for a wide range of conjugated polymers, in particular, donor-acceptor (D-A)-type polymers. Herein we examine the effect of fluorination on the device performance of solar cells as a function of the position of fluorination (on the acceptor unit or on the donor unit), aiming to outline a clear understanding of the benefits of this curious substituent. As fluorination of the acceptor unit is the most adopted strategy for D-A polymers, we first discuss the effect of fluorination of the acceptor units, highlighting the five most widely utilized acceptor units. While improved device efficiency has been widely observed with fluorinated acceptor units, the underlying reasons vary from case to case and highly depend on the chemical structure of the polymer. Second, the effect of fluorination of the donor unit is addressed. Here we focus on four donor units that have been most studied with fluorination. While device-performance-enhancing effects by fluorination of the donor units have also been observed, it is less clear that fluorine will always benefit the efficiency of the OSC, as there are several cases where the efficiency drops, in particular with "over-fluorination", i.e., when

  3. Carrier Transport Enhancement in Conjugated Polymers through Interfacial Self-Assembly of Solution-State Aggregates

    KAUST Repository

    Zhao, Kui

    2016-07-13

    We demonstrate that local and long range orders of poly(3-hexylthiophene) (P3HT) semicrystalline films can be synergistically improved by combining chemical functionalization of the dielectric surface with solution-state disentanglement and pre-aggregation of P3HT in a theta solvent, leading to a very significant enhancement of the field effect carrier mobility. The pre-aggregation and surface functionalization effects combine to enhance the carrier mobility nearly 100-fold as compared with standard film preparation by spin-coating, and nearly 10-fold increase over the benefits of pre-aggregation alone. In situ quartz crystal microbalance with dissipation (QCM-D) experiments reveal enhanced deposition of pre-aggregates on surfaces modified with an alkyl-terminated self-assembled monolayer (SAM) in comparison to un-aggregated polymer chains. Additional investigations reveal the combined pre-aggregation and surface functionalization significantly enhances local order of the conjugated polymer through planarization and extension of the conjugated backbone of the polymer which clearly translate to significant improvements of carrier transport at the semiconductor-dielectric interface in organic thin film transistors. This study points to opportunities in combining complementary routes, such as well-known pre-aggregation with substrate chemical functionalization, to enhance the polymer self-assembly and improve its interfacial order with benefits for transport properties.

  4. Investigation on structural, optical and electrical properties of polythiophene-Al2O3 composites

    Science.gov (United States)

    Vijeth, H.; Yesappa, L.; Niranjana, M.; Ashokkumar, S. P.; Devendrappa, H.

    2018-05-01

    The polythiophene (PTH) and polythiophene-Al2O3 composites prepared by in situ chemical polymerisation in the presence of anionic surfactant camphor sulfonic acid (CSA). The formation of composite is confirmed by X-ray Diffraction (XRD) and Energy Dispersive X-ray spectroscopy (EDX) analysis. The surface morphology was studied using Field Emission Electron Microscopy (FESEM). Optical properties was studied using UV-visible spectroscopy, it observed decrease in the band gap reveals material has potential application in optical devices. The dielectric constant and AC conductivity of composite have been studied for different temperature in the frequency range 1 kHz -1 MHz.

  5. Sensitization of nano-porous ZnO photo-anode by a conjugated conducting polymer

    Energy Technology Data Exchange (ETDEWEB)

    Sirimanne, P.M. [Nano-Science Laboratory, Institute of Fundamental Studies, Hantana Road, Kandy (Sri Lanka); Environmental and Renewable Energy Systems Division, Graduate School of Engineering, Gifu University, 1-1 Yanagido, Gifu 501-1193 (Japan); Premalal, E.V.A. [Nano-Science Laboratory, Institute of Fundamental Studies, Hantana Road, Kandy (Sri Lanka); Minoura, H. [Environmental and Renewable Energy Systems Division, Graduate School of Engineering, Gifu University, 1-1 Yanagido, Gifu 501-1193 (Japan)

    2011-01-15

    Hybrid ZnO films are prepared via one-step electrochemical process. Extraction of organic component from hybrid films results tiny wires like ZnO columns perpendicular to the substrate. Visible light sensitive-conjugated polymer poly(2-methoxy-5-[2 ethylhexyloxy]-1-4-phenylenevinylene, MEH-PPV) was embedded in highly porous ZnO ceramic by a solvent vaporization technique. An attempt was made to fabricate polymer sensitized photovoltaic cell by coupling polymer embedded ZnO electrodes with an electrolyte. Maximum photovoltage of 490 mV is observed for the cell with the configuration of ZnO vertical stroke MEH-PPV vertical stroke I{sup -}/I{sub 3}{sup -} cell. (author)

  6. Adaptive sliding mode control of tri-layer conjugated polymer actuators

    International Nuclear Information System (INIS)

    Wang, Xiangjiang; Alici, Gursel; Nguyen, Chuc Huu

    2013-01-01

    This paper proposes an adaptive sliding mode control methodology to enhance the positioning ability of conducting polymer actuators typified by tri-layer conjugated polymer actuators. This is motivated by the search for an effective control strategy to command such actuators to a desired configuration in the presence of parametric uncertainties and unmodeled disturbances. After analyzing the stability of the adaptive sliding mode control system, experiments were conducted to demonstrate its satisfactory tracking ability, based on a series of experimental results. Implementation of the control law requires a valid model of the conducting polymer actuator and boundaries of the uncertainties and disturbances. Based on the theoretical and experimental results presented, the adaptive sliding mode control methodology is very attractive in the field of smart actuators which contain significant uncertainties and disturbances. (paper)

  7. Effect of side chain length on charge transport, morphology, and photovoltaic performance of conjugated polymers in bulk heterojunction solar cells

    NARCIS (Netherlands)

    Duan, C.; Willems, R.E.M.; van Franeker, J.J.; Bruijnaers, B.J.; Wienk, M.M.; Janssen, R.A.J.

    2016-01-01

    The effect of side chain length on the photovoltaic properties of conjugated polymers is systematically investigated with two sets of polymers that bear different alkyl side chain lengths based on benzodithiophene and benzo[2,1,3]thiadiazole or 5,6-difluorobenzo[2,1,3]thiadiazole. Characterization

  8. The Influence of Conjugated Polymer Side Chain Manipulation on the Efficiency and Stability of Polymer Solar Cells

    DEFF Research Database (Denmark)

    Heckler, Ilona Maria; Kesters, Jurgen; Defour, Maxime

    2016-01-01

    ]thiazole (TzTz) acceptor units, were selected toward effective device scalability by roll-coating. The influence of the partial exchange (5% or 10%) of the solubilizing 2-hexyldecyloxy by alternative 2-phenylethoxy groups on efficiency and stability was investigated. With an increasing 2-phenylethoxy ratio...... studies under constant sun irradiance showed a diminishing initial degradation rate for the BT-based devices upon including the alternative side chains, whereas the (more stable) TzTz-based devices degraded at a faster rate from the start of the experiment upon partly exchanging the side chains. No clear......The stability of polymer solar cells (PSCs) can be influenced by the introduction of particular moieties on the conjugated polymer side chains. In this study, two series of donor-acceptor copolymers, based on bis(thienyl)dialkoxybenzene donor and benzo[c][1,2,5]thiadiazole (BT) or thiazolo[5,4-d...

  9. Photonic effects in microstructured conjugated polymer films and light emitting diodes

    International Nuclear Information System (INIS)

    Matterson, B.J.

    2002-03-01

    This thesis reports an investigation into the photonic effects caused by wavelength scale microstructure patterned onto films of conjugated polymers. The efficiency of light emitting diodes (LEDs) made from conjugated polymers is limited in part by the trapping of light into waveguide modes caused by the high refractive index of these materials. Waveguide modes in films of poly(p,-phenylene vinylene) (PPV) and poly(2-methoxy, 5-(2'ethylhexyloxy)-p-phenylene vinylene) (MEH-PPV) are analysed and the refractive index of these materials is calculated. The photoluminescence of conjugated polymer films that have been spun onto textured substrates is analysed. It is found that the photoluminescence quantum yield of a film spun onto a substrate inscribed with a grating is increased. It is also found that the photoluminescence spectrum of the film is dramatically altered and varies substantially with viewing angle. The features in the spectrum caused by the grating are strongly polarized. These effects are analysed and are attributed to the scattering of waveguided light out of the film. It is found that films spun onto metal gratings exhibit especially strong scattering. The effect of metal gratings with various grating depths is analysed. The possible contribution of band gaps to the photoluminescence spectrum from polymers on strong metal gratings is discussed. LEDs that include grating structures are constructed and analysed. It is found that having grating structures on the metal layers that are used as electrodes in the LED does not adversely affect the electrical properties of the LED. It is demonstrated that grating in the LED is able to substantially increase the light emission without using extra electrical power. The emission spectra from LEDs are observed to vary with angle, and exhibit considerable polarization. (author)

  10. Molecular Orientation of Conjugated Polymer Chains in Nanostructures and Thin Films: Review of Processes and Application to Optoelectronics

    Directory of Open Access Journals (Sweden)

    Varun Vohra

    2017-01-01

    Full Text Available Semiconducting polymers are composed of elongated conjugated polymer backbones and side chains with high solubility and mechanical properties. The combination of these two features results in a high processability and a potential to orient the conjugated backbones in thin films and nanofibers. The thin films and nanofibers are usually composed of highly crystalline (high charge transport and amorphous parts. Orientation of conjugated polymer can result in enhanced charge transport or optical properties as it induces increased crystallinity or preferential orientation of the crystallites. After summarizing the potential strategies to exploit molecular order in conjugated polymer based optoelectronic devices, we will review some of the fabrication processes to induce molecular orientation. In particular, we will review the cases involving molecular and interfacial interactions, unidirectional deposition processes, electrospinning, and postdeposition mechanical treatments. The studies presented here clearly demonstrate that process-controlled molecular orientation of the conjugated polymer chains can result in high device performances (mobilities over 40 cm2·V−1·s−1 and solar cells with efficiencies over 10%. Furthermore, the peculiar interactions between molecularly oriented polymers and polarized light have the potential not only to generate low-cost and low energy consumption polarized light sources but also to fabricate innovative devices such as solar cell integrated LCDs or bipolarized LEDs.

  11. Elucidation of the Structure Formation of Polymer-Conjugated Proteins in Solution and Block Copolymer Templates

    Science.gov (United States)

    Ferebee, Rachel L.

    The broader technical objective of this work is to contribute to the development of enzyme-functionalized nanoporous membranes that can function as autonomous and target selective dynamic separators. The scientific objective of the research performed within this thesis is to elucidate the parameters that control the mixing of proteins in organic host materials and in block copolymers templates in particular. A "biomimetic" membrane system that uses enzymes to selectively neutralize targets and trigger a change in permeability of nanopores lined with a pH-responsive polymer has been fabricated and characterized. Mechanical and functional stability, as well as scalability, have been demonstrated for this system. Additional research has focused on the role of polymeric ligands on the solubility characteristics of the model protein, Bovine Serum Albumin (BSA). For this purpose BSA was conjugated with poly(ethylene glycol) (PEG) ligands of varied degree of polymerization and grafting density. Combined static and dynamic light scattering was used (in conjunction with MALDI-TOF) to determine the second virial coefficient in PBS solutions. At a given mass fraction PEG or average number of grafts, the solubility of BSA-PEG conjugates is found to increase with the degree of polymerization of conjugated PEG. This result informs the synthesis of protein-conjugate systems that are optimized for the fabrication of block copolymer blend materials with maximum protein loading. Blends of BSA-PEG conjugates and block copolymer (BCP) matrices were fabricated to evaluate the dispersion morphology and solubility limits in a model system. Electron microscopy was used to evaluate the changes in lamellar spacing with increased filling fraction of BSA-PEG conjugates.

  12. Acyclic Diene Metathesis (ADMET Polymerization for Precise Synthesis of Defect-Free Conjugated Polymers with Well-Defined Chain Ends

    Directory of Open Access Journals (Sweden)

    Tahmina Haque

    2015-03-01

    Full Text Available This accounts introduces unique characteristics by adopting the acyclic diene metathesis (ADMET polymerization for synthesis of conjugated polymers, poly(arylene vinylenes, known as promising molecular electronics. The method is more suitable than the other methods in terms of atom efficiency affording defect-free, stereo-regular (exclusive trans polymers with well-defined chain ends; the resultant polymers possess better property than those prepared by the conventional methods. The chain ends (vinyl group in the resultant polymer prepared by ruthenium-carbene catalyst(s can be modified by treating with molybdenum-alkylidene complex (olefin metathesis followed by addition of various aldehyde (Wittig type cleavage, affording the end-functionalized polymers exclusively. An introduction of initiating fragment, the other conjugated segment, and one-pot synthesis of end-functionalized block copolymers, star shape polymers can be achieved by adopting this methodology.

  13. Charge transport behavior of benodithiophene-diketopyrrololpyrrole-based conjugated polymer in organic field-effect transistors

    Energy Technology Data Exchange (ETDEWEB)

    Park, Jin Kuen [Dept. of Chemistry, Hankuk University of Foreign Studies, Yongin (Korea, Republic of)

    2015-07-15

    Organic optoelectronic devices, such as light-emitting diodes, organic solar cells (OSCs), and organic field effect transistors (OFETs), have emerged due to the development of π-conjugated polymers. Because the delocalized π-framework can significantly reduce the energy gap between the highest-occupied molecular orbital (HOMO) and the lowest-unoccupied molecular orbital (LUMO), their intrinsic optoelectronic properties can be tunable with their conjugation length in terms of average molecular weights and their π-backbone structures. The new type of low bandgap conjugated polymer (P1) has been successively polymerized via a palladium- catalyzed Stille cross-coupling reaction with bis-ethylhexyl BDT and bis-n-decane DPP. With a linear alkyl chain in the DPP units, the intermolecular packing structure was thought to be enhanced by proving the UV–Vis and UPS spectra. In addition, the electronic properties of P1 via field-effect transistors well illustrate the typical p-type semiconducting property without showing the significant improvement by thermal annealing. From a broader perspective, this research indicates that a wider choice of linear alkyl chain length in DPP units and modification of the interface between dielectric and active layers should be sought to further optimize device performance. Hence, progressive works with the strategy presented in this report will be pursued to address the different challenges in attaining target OFET performances.

  14. Roughening Conjugated Polymer Surface for Enhancing the Charge Collection Efficiency of Sequentially Deposited Polymer/Fullerene Photovoltaics

    Directory of Open Access Journals (Sweden)

    Yoonhee Jang

    2015-08-01

    Full Text Available A method that enables the formation of a rough nano-scale surface for conjugated polymers is developed through the utilization of a polymer chain ordering agent (OA. 1-Chloronaphthalene (1-CN is used as the OA for the poly(3-hexylthiophene-2,5-diyl (P3HT layer. The addition of 1-CN to the P3HT solution improves the chain ordering of the P3HT during the film formation process and increases the surface roughness of the P3HT film compared to the film prepared without 1-CN. The roughened surface of the P3HT film is utilized to construct a P3HT/fullerene bilayer organic photovoltaic (OPV by sequential solution deposition (SqSD without thermal annealing process. The power conversion efficiency (PCE of the SqSD-processed OPV utilizing roughened P3HT layer is 25% higher than that utilizing a plain P3HT layer. It is revealed that the roughened surface of the P3HT increases the heterojunction area at the P3HT/fullerene interface and this resulted in improved internal charge collection efficiency, as well as light absorption efficiency. This method proposes a novel way to improve the PCE of the SqSD-processed OPV, which can be applied for OPV utilizing low band gap polymers. In addition, this method allows for the reassessment of polymers, which have shown insufficient performance in the BSD process.

  15. The Influence of Conjugated Polymer Side Chain Manipulation on the Efficiency and Stability of Polymer Solar Cells.

    Science.gov (United States)

    Heckler, Ilona M; Kesters, Jurgen; Defour, Maxime; Madsen, Morten V; Penxten, Huguette; D'Haen, Jan; Van Mele, Bruno; Maes, Wouter; Bundgaard, Eva

    2016-03-09

    The stability of polymer solar cells (PSCs) can be influenced by the introduction of particular moieties on the conjugated polymer side chains. In this study, two series of donor-acceptor copolymers, based on bis(thienyl)dialkoxybenzene donor and benzo[ c ][1,2,5]thiadiazole (BT) or thiazolo[5,4- d ]thiazole (TzTz) acceptor units, were selected toward effective device scalability by roll-coating. The influence of the partial exchange (5% or 10%) of the solubilizing 2-hexyldecyloxy by alternative 2-phenylethoxy groups on efficiency and stability was investigated. With an increasing 2-phenylethoxy ratio, a decrease in solar cell efficiency was observed for the BT-based series, whereas the efficiencies for the devices based on the TzTz polymers remained approximately the same. The photochemical degradation rate for PSCs based on the TzTz polymers decreased with an increasing 2-phenylethoxy ratio. Lifetime studies under constant sun irradiance showed a diminishing initial degradation rate for the BT-based devices upon including the alternative side chains, whereas the (more stable) TzTz-based devices degraded at a faster rate from the start of the experiment upon partly exchanging the side chains. No clear trends in the degradation behavior, linked to the copolymer structural changes, could be established at this point, evidencing the complex interplay of events determining PSCs' lifetime.

  16. The Influence of Conjugated Polymer Side Chain Manipulation on the Efficiency and Stability of Polymer Solar Cells

    Directory of Open Access Journals (Sweden)

    Ilona M. Heckler

    2016-03-01

    Full Text Available The stability of polymer solar cells (PSCs can be influenced by the introduction of particular moieties on the conjugated polymer side chains. In this study, two series of donor-acceptor copolymers, based on bis(thienyldialkoxybenzene donor and benzo[c][1,2,5]thiadiazole (BT or thiazolo[5,4-d]thiazole (TzTz acceptor units, were selected toward effective device scalability by roll-coating. The influence of the partial exchange (5% or 10% of the solubilizing 2-hexyldecyloxy by alternative 2-phenylethoxy groups on efficiency and stability was investigated. With an increasing 2-phenylethoxy ratio, a decrease in solar cell efficiency was observed for the BT-based series, whereas the efficiencies for the devices based on the TzTz polymers remained approximately the same. The photochemical degradation rate for PSCs based on the TzTz polymers decreased with an increasing 2-phenylethoxy ratio. Lifetime studies under constant sun irradiance showed a diminishing initial degradation rate for the BT-based devices upon including the alternative side chains, whereas the (more stable TzTz-based devices degraded at a faster rate from the start of the experiment upon partly exchanging the side chains. No clear trends in the degradation behavior, linked to the copolymer structural changes, could be established at this point, evidencing the complex interplay of events determining PSCs’ lifetime.

  17. Polymer-Block-Polypeptides and Polymer-Conjugated Hybrid Materials as Stimuli-Responsive Nanocarriers for Biomedical Applications.

    Science.gov (United States)

    John, Johnson V; Johnson, Renjith P; Heo, Min Seon; Moon, Byeong Kyu; Byeon, Seong Jin; Kim, Il

    2015-01-01

    Stimuli-responsive nanocarriers are a class of soft materials that includes natural polymers, synthetic polymers, and polypeptides. Recently, modern synthesis tools such as atom transfer radical polymerization, reversible addition-fragmentation chain transfer polymerization, nitroxide-mediated radical polymerization, ring-opening polymerization of α-amino acid N-carboxyanhydrides, and various "click" chemistry strategies were simultaneously employed for the design and synthesis of nanosized drug delivery vehicles. Importantly, the research focused on the improvement of the nanocarrier targetability and the site-specific, triggered release of therapeutics with high drug loading efficiency and minimal drug leakage during the delivery to specific targets. In this context, nanocarriers responsive to common stimuli such as pH, temperature, redox potential, light, etc. have been widely used for the controlled delivery of therapeutics to pathological sites. Currently, different synthesis and self-assembly strategies improved the drug loading efficacy and targeted delivery of therapeutic agents to the desired site. In particular, polypeptide-containing hybrid materials have been developed for the controlled delivery of therapeutic agents. Therefore, stimuli-sensitive synthetic polypeptide-based materials have been extensively investigated in recent years. This review focuses on recent advances in the development of polymer-block-polypeptides and polymer-conjugated hybrid materials that have been designed and evaluated for various stimuli-responsive drug and gene delivery applications.

  18. Theory of interfacial charge-transfer complex photophysics in π-conjugated polymer-fullerene blends

    Science.gov (United States)

    Aryanpour, K.; Psiachos, D.; Mazumdar, S.

    2010-03-01

    We present a theory of the electronic structure and photophysics of 1:1 blends of derivatives of polyparaphenylenevinylene and fullerenes [1]. Within the same Coulomb-correlated Hamiltonian applied previously to interacting chains of single-component π-conjugated polymers [2], we find an exciplex state that occurs below the polymer's optical exciton. Weak absorption from the ground state occurs to the exciplex. We explain transient photoinduced absorptions in the blend [3], observed for both above-gap and below-gap photoexcitations, within our theory. Photoinduced absorptions for above-gap photoexcitation are from the optical exciton as well as the exciplex, while for below-gap photoexcitation induced absorptions are from the exciplex alone. In neither case are free polarons generated in the time scale of the experiment. Importantly, the photophysics of films of single-component π-conjugated polymers and blends can both be understood by extending Mulliken's theory of ground state charge-transfer to the case of excited state charge-transfer. [1] K. Aryanpour, D. Psiachos, and S. Mazumdar, arXiv:0908.0366 [2] D. Psiachos and S. Mazumdar, Phys. Rev. B. 79 155106 (2009) [3] T. Drori et al., Phys. Rev. Lett. 101, 037402 (2008)

  19. A two-dimensional conjugated aromatic polymer via C-C coupling reaction

    Science.gov (United States)

    Liu, Wei; Luo, Xin; Bao, Yang; Liu, Yan Peng; Ning, Guo-Hong; Abdelwahab, Ibrahim; Li, Linjun; Nai, Chang Tai; Hu, Zhi Gang; Zhao, Dan; Liu, Bin; Quek, Su Ying; Loh, Kian Ping

    2017-06-01

    The fabrication of crystalline 2D conjugated polymers with well-defined repeating units and in-built porosity presents a significant challenge to synthetic chemists. Yet they present an appealing target because of their desirable physical and electronic properties. Here we report the preparation of a 2D conjugated aromatic polymer synthesized via C-C coupling reactions between tetrabromopolyaromatic monomers. Pre-arranged monomers in the bulk crystal undergo C-C coupling driven by endogenous solid-state polymerization to produce a crystalline polymer, which can be mechanically exfoliated into micrometre-sized lamellar sheets with a thickness of 1 nm. Isothermal gas-sorption measurements of the bulk material reveal a dominant pore size of ~0.6 nm, which indicates uniform open channels from the eclipsed stacking of the sheets. When employed as an organic anode in an ambient-temperature sodium cell, the material allows a fast charge/discharge of sodium ions, with impressive reversible capacity, rate capability and stability metrics.

  20. Color tunable hybrid light-emitting diodes based on perovskite quantum dot/conjugated polymer

    Science.gov (United States)

    Germino, José C.; Yassitepe, Emre; Freitas, Jilian N.; Santiago, Glauco M.; Bonato, Luiz Gustavo; de Morais, Andréia; Atvars, Teresa D. Z.; Nogueira, Ana F.

    2017-08-01

    Inorganic organic metal halide perovskite materials have been investigated for several technological applications, such as photovoltaic cells, lasers, photodetectors and light emitting diodes (LEDs), either in the bulk form or as colloidal nanoparticles. Recently, all inorganic Cesium Lead Halide (CsPbX3, X=Cl,Br, I) perovskite quantum dots (PQDs) were reported with high photoluminescence quantum yield with narrow emission lines in the visible wavelengths. Here, green-emitting perovskite quantum dots (PQDs) prepared by a synthetic method based on a mixture of oleylamine and oleic acid as surfactants were applied in the electroluminescent layer of hybrid LEDs in combination with two different conjugated polymers: polyvinylcarbazole (PVK) or poly(9,9-di-n-octylfluorenyl-2,7-diyl) (PFO). The performance of the diodes and the emission color tuning upon dispersion of different concentrations of the PQDs in the polymer matrix is discussed. The presented approach aims at the combination of the optical properties of the PQDs and their interaction with wide bandgap conjugated polymers, associated with the solution processing ability of these materials.

  1. Structural Modifications and Photophysical Studies of Fluorescent Conjugated Polymers for Solid State Sensor Development

    Science.gov (United States)

    Chen, Anting

    Fluorescent conjugated polymers (FCPs) represent an exciting area of research in chemosensors and biosensors. Previously, the polymer tmeda-PPETE, N,N,N'-trimethylethylenediamino (tmeda) receptors on a poly[2,5-thiophenediyl-1,2-ethynediyl-1,4-phenylenediyl-1,2-ethynediyl] (PPETE) backbone, showed significant quenching when copper(II) was added. Tmeda-PPETE polymer preloaded with copper(II) was found to be a fluorescent "turn-on" sensor for iron cations. Additional investigation of this metallopolymer revealed a selective sensory system toward carbonate and phosphorus anions through a competitive binding of copper(II) between the polymer tmeda-PPETE and the anions. Fluorescent turn-on response under systematically varied pH was affected by the equilibrium shift of the ionization of polyprotic ions. A sterically hindered pentiptycene group was introduced to the PPETE polymer backbone aiming to reduce aggregation and self-quenching in the solid state. A new FCP, tmeda-PPpETE (poly[(pentiptycene ethynylene)-alt-(thienylene ethynylene)] with tmeda receptors, has been designed and synthesized via Sonogashira cross-coupling reaction. Absorption and emission spectra of tmeda-PPpETE showed blue shifting from tmeda-PPETE, suggesting increased rigidity of polymer backbone. Tmeda-PPpETE showed a high selectivity towards copper(II) with improved sensitivity compared to tmeda-PPETE. The fluorescent quenching response is over 120-fold at emission maximum, and the detection limit is 1.04 ppb, significantly lower than the EPA action level of 1.3 ppm for copper(II). A small turn-off fluorescent response of tmeda-PPpETE was also observed upon addition of iron cations. To further investigate the interaction between pentiptycene containing polymers and iron cations, tmpda-PPpETE containing N,N,N'-trimethylpropylenediamino (tmpda) receptors was designed and synthesized. The absorption and emission spectra for tmpda-PPpETE were analogous to those of tmeda-PPpETE, with a higher quantum

  2. Effect of introduction of chondroitin sulfate into polymer-peptide conjugate responding to intracellular signals

    Science.gov (United States)

    Tomiyama, Tetsuro; Toita, Riki; Kang, Jeong-Hun; Koga, Haruka; Shiosaki, Shujiro; Mori, Takeshi; Niidome, Takuro; Katayama, Yoshiki

    2011-09-01

    We recently developed a novel tumor-targeted gene delivery system responding to hyperactivated intracellular signals. Polymeric carrier for gene delivery consists of hydrophilic neutral polymer as main chains and cationic peptide substrate for target enzyme as side chains, and was named polymer-peptide conjugate (PPC). Introduction of chondroitin sulfate (CS), which induces receptor-medicated endocytosis, into polymers mainly with a high cationic charge density such as polyethylenimine can increase tumor-targeted gene delivery. In the present study, we examined whether introduction of CS into PPC containing five cationic amino acids can increase gene expression in tumor cells. Size and zeta potential of plasmid DNA (pDNA)/PPC/CS complex were <200 nm and between -10 and -15 mV, respectively. In tumor cell experiments, pDNA/PPC/CS complex showed lower stability and gene regulation, compared with that of pDNA/PPC. Moreover, no difference in gene expression was identified between positive and negative polymer. These results were caused by fast disintegration of pDNA/PPC/CS complexes in the presence of serum. Thus, we suggest that introduction of negatively charged CS into polymers with a low charge density may lead to low stability and gene regulation of complexes.

  3. Real-time observation of conformational switching in single conjugated polymer chains.

    Science.gov (United States)

    Tenopala-Carmona, Francisco; Fronk, Stephanie; Bazan, Guillermo C; Samuel, Ifor D W; Penedo, J Carlos

    2018-02-01

    Conjugated polymers (CPs) are an important class of organic semiconductors that combine novel optoelectronic properties with simple processing from organic solvents. It is important to study CP conformation in solution to understand the physics of these materials and because it affects the properties of solution-processed films. Single-molecule techniques are unique in their ability to extract information on a chain-to-chain basis; however, in the context of CPs, technical challenges have limited their general application to host matrices or semiliquid environments that constrain the conformational dynamics of the polymer. We introduce a conceptually different methodology that enables measurements in organic solvents using the single-end anchoring of polymer chains to avoid diffusion while preserving polymer flexibility. We explore the effect of organic solvents and show that, in addition to chain-to-chain conformational heterogeneity, collapsed and extended polymer segments can coexist within the same chain. The technique enables real-time solvent-exchange measurements, which show that anchored CP chains respond to sudden changes in solvent conditions on a subsecond time scale. Our results give an unprecedented glimpse into the mechanism of solvent-induced reorganization of CPs and can be expected to lead to a new range of techniques to investigate and conformationally manipulate CPs.

  4. Hepatoma targeting peptide conjugated bio-reducible polymer complexed with oncolytic adenovirus for cancer gene therapy.

    Science.gov (United States)

    Choi, Joung-Woo; Kim, Hyun Ah; Nam, Kihoon; Na, Youjin; Yun, Chae-Ok; Kim, SungWan

    2015-12-28

    Despite adenovirus (Ad) vector's numerous advantages for cancer gene therapy, such as high ability of endosomal escape, efficient nuclear entry mechanism, and high transduction, and therapeutic efficacy, tumor specific targeting and antiviral immune response still remain as a critical challenge in clinical setting. To overcome these obstacles and achieve cancer-specific targeting, we constructed tumor targeting bioreducible polymer, an arginine grafted bio-reducible polymer (ABP)-PEG-HCBP1, by conjugating PEGylated ABP with HCBP1 peptides which has high affinity and selectivity towards hepatoma. The ABP-PEG-HCBP1-conjugated replication incompetent GFP-expressing ad, (Ad/GFP)-ABP-PEG-HCBP1, showed a hepatoma cancer specific uptake and transduction compared to either naked Ad/GFP or Ad/GFP-ABP. Competition assays demonstrated that Ad/GFP-ABP-PEG-HCBP1-mediated transduction was specifically inhibited by HCBP1 peptide rather than coxsackie and adenovirus receptor specific antibody. In addition, ABP-PEG-HCBP1 can protect biological activity of Ad against serum, and considerably reduced both innate and adaptive immune response against Ad. shMet-expressing oncolytic Ad (oAd; RdB/shMet) complexed with ABP-PEG-HCBP1 delivered oAd efficiently into hepatoma cancer cells. The oAd/ABP-PEG-HCBP1 demonstrated enhanced cancer cell killing efficacy in comparison to oAd/ABP complex. Furthermore, Huh7 and HT1080 cancer cells treated with oAd/shMet-ABP-PEG-HCBP1 complex had significantly decreased Met and VEGF expression in hepatoma cancer, but not in non-hepatoma cancer. In sum, these results suggest that HCBP1-conjugated bioreducible polymer could be used to deliver oncolytic Ad safely and efficiently to treat hepatoma. Copyright © 2015 Elsevier B.V. All rights reserved.

  5. Modelling of charge carrier transport in conjugated polymers doped by polar additives

    Czech Academy of Sciences Publication Activity Database

    Toman, Petr; Nešpůrek, Stanislav; Bartkowiak, W.

    2009-01-01

    Roč. 27, č. 3 (2009), s. 797-812 ISSN 0137-1339. [International Conference on Electrical and Related Properties of Organic Solids /11./. Piechowice, 13.07.2008-17.07.2008] R&D Projects: GA ČR GA203/06/0285; GA AV ČR KAN400720701; GA MŠk MEB050815 Institutional research plan: CEZ:AV0Z40500505 Keywords : conjugated polymers * charge carrier transport * molecular electronics Subject RIV: CD - Macromolecular Chemistry Impact factor: 0.384, year: 2009

  6. Diffuse x-ray scattering study of interfacial structure of self-assembled conjugated polymers

    International Nuclear Information System (INIS)

    Wang Jun; Park, Y.J.; Lee, K.-B.; Hong, H.; Davidov, D.

    2002-01-01

    The interfacial structures of self-assembled heterostructures through alternate deposition of conjugated and nonconjugated polymers were studied by x-ray reflectivity and nonspecular scattering. We found that the interfacial width including the effects of both interdiffusion and interfacial roughness (correlated) was mainly contributed by the latter one. The self-assembled deposition induced very small interdiffusion between layers. The lateral correlation length ξ parallel grew as a function of deposition time (or film thickness) described by a power law ξ parallel ∝t β/H and was also observed from the off-specular scattering

  7. Inkjet printing of conjugated polymer precursors on paper substrates for colorimetric sensing and flexible electrothermochromic display.

    Science.gov (United States)

    Yoon, Bora; Ham, Dae-Young; Yarimaga, Oktay; An, Hyosung; Lee, Chan Woo; Kim, Jong-Man

    2011-12-08

    Inkjet-printable aqueous suspensions of conjugated polymer precursors are developed for fabrication of patterned color images on paper substrates. Printing of a diacetylene (DA)-surfactant composite ink on unmodified paper and photopaper, as well as on a banknote, enables generation of latent images that are transformed to blue-colored polydiacetylene (PDA) structures by UV irradiation. Both irreversible and reversible thermochromism with the PDA printed images are demonstrated and applied to flexible and disposable sensors and to displays. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. Single-Molecule Luminescence and High Efficiency Photovoltaic Cells Based on Percolated Conducting Carbon Nanotubes Scaffolds Templated with Light-Harvesting Conjugated Polymers and Nanohybrids

    National Research Council Canada - National Science Library

    Yang, Arnold C

    2009-01-01

    .... Nanocomposites constructed by surface-grafted multiwall carbon nanotubes (CNTs) with conjugated polymers dispersed in a polymer matrix were synthesized to form novel optoelectronic materials that exploit single-molecule effects...

  9. Effects of chemical modifications on photophysics and exciton dynamics on {pi}-conjugation attenuated and metal-chelated photoconducting polymers

    Energy Technology Data Exchange (ETDEWEB)

    Chen, L. X.; Jager, W. J. H.; Gosztola, D. J.; Niemczyk, M. P.; Wasielewski, M. R.

    2000-03-11

    Effects of two types of chemical modifications on photoconducting polymers consisting of polyphenylenevinylene (PPV) derivatives are studied by static and ultrafast transient optical spectroscopy as well as semi-empirical ZINDO calculations. The first type of modification inserts 2,2{prime}-bipyridyl-5-vinylene units (bpy V) in the PPV backbone, and the second type involves metal-chelation with the bpy sites. Photoluminescence and exciton dynamics of polymers 1 and 2 with PV:bpyV ratios of 1 and 3 were examined in solution, and compared to those of the homopolymer, poly(2,5-bis(2{prime}-ethylhexyloxy)-1,4-phenylenevinylene) (BEH-PPV). Similar studies were carried out for several metal-chelated polymers. These results can be explained by changes in {pi}-conjugation throughout the polymer backbone. The attenuation in {pi}-conjugation by the chemical modifications transforms a conducting polymer from one-dimensional semiconductor to molecular aggregates.

  10. Non-covalent functionalization of single wall carbon nanotubes and graphene by a conjugated polymer

    KAUST Repository

    Jiwuer, Jilili

    2014-07-07

    We report first-principles calculations on the binding of poly[(9,9-bis-(6-bromohexylfluorene-2,7-diyl)-co-(benzene-1,4-diyl)] to a (8,0) single wall carbon nanotube (SWCNT) and to graphene. Considering different relative orientations of the subsystems, we find for the generalized gradient approximation a non-binding state, whereas the local density approximation predicts reasonable binding energies. The results coincide after inclusion of van der Waals corrections, which demonstrates a weak interaction between the polymer and SWCNT/graphene, mostly of van der Waals type. Accordingly, the density of states shows essentially no hybridization. The physisorption mechanism explains recent experimental observations and suggests that the conjugated polymer can be used for non-covalent functionalization.

  11. Thiazoloisoindigo: a Building Block that Merges the Merits of Thienoisoindigo and Diazaisoindigo for Conjugated Polymers.

    Science.gov (United States)

    Wan, Xiaobo; Li, Chenchen; Wang, Xiao; Hio-Ieng, Un; Peng, Jiawei; Lan, Zhenggang; Cai, Mian; Pei, Jian; Wang, Jieyu

    2018-04-24

    Thiazoloisoindigo, a novel structural variation of isoindigo, is for the first time utilized to synthesize conjugated polymers. Polymer based on thiazoloisoindigo merges the advantages of the one based on thienoisoindigo and diazaisoindigo: It not only exhibits a greatly red shifted UV-vis absorption to the near-infrared region due to its strong tendency to form quinoidal structures, similar to that based on thienoisoindigo, but also shows excellent ambipolar mobility (hole 3.93 and electron 1.07 cm2 V-1 s-1, respectively) in organic field-effect transistors (OFETs), superior than that based on diazaisoindigo, showing the strong electron-withdrawing capability of thiazoloisoindigo. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. pH-responsive fluorescence chemical sensor constituted by conjugated polymers containing pyridine rings.

    Science.gov (United States)

    Adachi, Naoya; Kaneko, Yuki; Sekiguchi, Kazuki; Sugiyama, Hiroki; Sugeno, Masafumi

    2015-12-01

    Poly(p-pyridinium phenylene ethynylene)s (PPyPE) functionalized with alternating donor-acceptor repeat units were synthesized by a Pd-catalyzed Sonogashira coupling reaction between diethynyl monomer and di-iodopyridine for use as a pH-responsive fluorescence chemical sensor. The synthesized PPyPE, containing pyridine units, was characterized by FT-IR, (1)H and (13)C NMR, UV-visible and fluorescence spectroscopies. We investigated the relationship between changes of optical properties and protonation/deprotonation of PPyPE containing pyridine units in solution. Addition of HCl decreased and red-shifted the fluorescence intensity of the conjugated polymers that contained pyridine rings; fluorescence intensity of the polymers increased upon addition of NaOH solution. The synthesized PPyPE was found to be an effective and reusable chemical sensor for pH sensing. Copyright © 2015 John Wiley & Sons, Ltd.

  13. Non-covalent functionalization of single wall carbon nanotubes and graphene by a conjugated polymer

    KAUST Repository

    Jiwuer, Jilili; Abdurahman, Ayjamal; Gü lseren, Oğuz; Schwingenschlö gl, Udo

    2014-01-01

    We report first-principles calculations on the binding of poly[(9,9-bis-(6-bromohexylfluorene-2,7-diyl)-co-(benzene-1,4-diyl)] to a (8,0) single wall carbon nanotube (SWCNT) and to graphene. Considering different relative orientations of the subsystems, we find for the generalized gradient approximation a non-binding state, whereas the local density approximation predicts reasonable binding energies. The results coincide after inclusion of van der Waals corrections, which demonstrates a weak interaction between the polymer and SWCNT/graphene, mostly of van der Waals type. Accordingly, the density of states shows essentially no hybridization. The physisorption mechanism explains recent experimental observations and suggests that the conjugated polymer can be used for non-covalent functionalization.

  14. Time Evolution of the Excimer State of a Conjugated Polymer Laser

    Directory of Open Access Journals (Sweden)

    Wafa Musa Mujamammi

    2017-11-01

    Full Text Available An excited dimer is an important complex formed in nano- or pico-second time scales in many photophysics and photochemistry applications. The spectral and temporal profile of the excimer state of a laser from a new conjugated polymer, namely, poly (9,9-dioctylfluorenyl-2,7-diyl (PFO, under several concentrations in benzene were investigated. These solutions were optically pumped by intense pulsed third-harmonic Nd:YAG laser (355-nm to obtain the amplified spontaneous emission (ASE spectra of a monomer and an excimer with bandwidths of 6 and 7 nm, respectively. The monomer and excimer ASEs were dependent on the PFO concentration, pump power, and temperature. Employing a sophisticated picosecond spectrometer, the time evolution of the excimer state of this polymer, which is over 400 ps, can be monitored.

  15. Anthracene-containing wide-band-gap conjugated polymers for high-open-circuit-voltage polymer solar cells.

    Science.gov (United States)

    Gong, Xue; Li, Cuihong; Lu, Zhen; Li, Guangwu; Mei, Qiang; Fang, Tao; Bo, Zhishan

    2013-07-25

    The synthesis, characterization, and photophysical and photovoltaic properties of two anthracene-containing wide-band-gap donor and acceptor (D-A) alternating conjugated polymers (P1 and P2) are described. These two polymers absorb in the range of 300-600 nm with a band gap of about 2.12 eV. Polymer solar cells with P1:PC71 BM as the active layer demonstrate a power conversion efficiency (PCE) of 2.23% with a high Voc of 0.96 V, a Jsc of 4.4 mA cm(-2) , and a comparable fill factor (FF) of 0.53 under simulated solar illumination of AM 1.5 G (100 mW cm(-2) ). In addition, P2:PC71 BM blend-based solar cells exhibit a PCE of 1.42% with a comparable Voc of 0.89 V, a Jsc of 3.0 mA cm(-2) , and an FF of 0.53. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. Electrical properties of a new sulfur-containing polymer for optoelectronic application

    Science.gov (United States)

    ElAkemi, ElMehdi; Jaballah, Nejmeddine; Ouada, Hafedh Ben; Majdoub, Mustapha

    2015-06-01

    An original polythiophene derivative was characterized to develop the optoelectronic properties of sulfur-containing π-conjugated polymer. The optical properties of the polymer were investigated by UV-visible absorption spectroscopy and atomic force microscopy. Investigations of the electrical characteristics of polymer diodes are reported. We present current-voltage characteristics and impedance spectroscopy measurements performed on partially sulfur-containing thin films in sandwich structure ITO/sulfur-containing polymer/Al. The conduction mechanisms in these layers are identified to be a space-charge-limited current. The AC electrical transport of the sulfur-containing polymer is studied as a function of frequency (100 Hz-10 MHz) and temperature in impedance spectroscopy analyses. We interpreted Cole-Cole plots in terms of the equivalent circuit model as a single parallel resistance and a capacitance network in series with a relatively small resistance. The evolution of the electrical parameters deduced from fitting of the experimental data is discussed.

  17. Well-defined degradable brush polymer-drug conjugates for sustained delivery of Paclitaxel.

    Science.gov (United States)

    Yu, Yun; Chen, Chih-Kuang; Law, Wing-Cheung; Mok, Jorge; Zou, Jiong; Prasad, Paras N; Cheng, Chong

    2013-03-04

    To achieve a conjugated drug delivery system with high drug loading but minimal long-term side effects, a degradable brush polymer-drug conjugate (BPDC) was synthesized through azide-alkyne click reaction of acetylene-functionalized polylactide (PLA) with azide-functionalized paclitaxel (PTXL) and poly(ethylene glycol) (PEG). Well-controlled structures of the resulting BPDC and its precursors were verified by (1)H NMR and gel permeation chromatography (GPC) characterizations. With nearly quantitative click efficiency, drug loading amount of the BPDC reached 23.2 wt %. Both dynamic light scattering (DLS) analysis and transmission electron microscopy (TEM) imaging indicated that the BPDC had a nanoscopic size around 10-30 nm. The significant hydrolytic degradability of the PLA backbone of the BPDC was confirmed by GPC analysis of its incubated solution. Drug release study showed that PTXL moieties can be released through the cleavage of the hydrolyzable conjugation linkage in pH 7.4 at 37 °C, with 50% release in about 22 h. As illustrated by cytotoxicity study, while the polymeric scaffold of the BPDC is nontoxic, the BPDC exhibited higher therapeutic efficacy toward MCF-7 cancer cells than free PTXL at 0.1 and 1 μg/mL. Using Nile red as encapsulated fluorescence probe, cell uptake study showed effective internalization of the BPDC into the cells.

  18. Stiffness, strength and adhesion characterization of electrochemically deposited conjugated polymer films

    Science.gov (United States)

    Qu, Jing; Ouyang, Liangqi; Kuo, Chin-chen; Martin, David C.

    2015-01-01

    Conjugated polymers such as poly(3,4-ethylenedioxythiphene) (PEDOT) are of interest for a variety of applications including interfaces between electronic biomedical devices and living tissue. The mechanical properties, strength, and adhesion of these materials to solid substrates are all vital for long-term applications. We have been developing methods to quantify the mechanical properties of conjugated polymer thin films. In this study the stiffness, strength and the interfacial shear strength (adhesion) of electrochemically deposited PEDOT and PEDOT-co-1,3,5-tri[2-(3,4-ethylene dioxythienyl)]-benzene (EPh) were studied. The estimated Young’s modulus of the PEDOT films was 2.6 ± 1.4 GPa, and the strain to failure was around 2%. The tensile strength was measured to be 56 ± 27 MPa. The effective interfacial shear strength was estimated with a shear-lag model by measuring the crack spacing as a function of film thickness. For PEDOT on gold/palladium-coated hydrocarbon film substrates an interfacial shear strength of 0.7 ± 0.3 MPa was determined. The addition of 5 mole% of a tri-functional EDOT crosslinker (EPh) increased the tensile strength of the films to 283 ± 67 MPa, while the strain to failure remained about the same (2%). The effective interfacial shear strength was increased to 2.4 ± 0.6 MPa. PMID:26607768

  19. Theory of even-parity states and two-photon spectra of conjugated polymers

    Science.gov (United States)

    McWilliams, P. C. M.; Hayden, G. W.; Soos, Z. G.

    1991-04-01

    The two-photon absorption (TPA) spectrum of interacting π electrons in conjugated polymers is shown to be qualitatively different from any single-particle description, including the Hartree-Fock limit. Alternating transfer integrals t(1+/-δ) along the backbone lead to a weak TPA below the one-photon gap Eg for arbitrarily weak correlations at δ=0, for intermediate correlations at δ=0.07 in polyenes, and for strong correlations at any δtheory to Eg in the limit of strong correlations in Hubbard models and is around 1.5Eg for Pariser-Parr-Pople (PPP) parameters. The PPP model, which accounts for one- and two-photon excitations of finite polyenes, is extended to even-parity states in polydiacetylenes (PDA's), polyacetylene (PA), and polysilanes (PS's). Previous experimental data for PDA and PS support both the strong TPA above Eg and weak TPA slightly below Eg for δ=0.15 in PDA and above Eg for δ~0.3 in PS. The strong TPA expected around 1.5Eg in isolated PA strands shifts to ~Eg due to interchain π-electron dispersion forces. TPA intensities in correlated states are shown to reflect both ionicity and mean-square charge separation. The even-parity states of conjugated polymers, like those of polyenes, show qualitatively different features associated with electron-electron correlations.

  20. RIR-MAPLE deposition of conjugated polymers and hybrid nanocomposites for application to optoelectronic devices

    International Nuclear Information System (INIS)

    Stiff-Roberts, Adrienne D.; Pate, Ryan; McCormick, Ryan; Lantz, Kevin R.

    2012-01-01

    Resonant infrared matrix-assisted pulsed laser evaporation (RIR-MAPLE) is a variation of pulsed laser deposition that is useful for organic-based thin films because it reduces material degradation by selective absorption of infrared radiation in the host matrix. A unique emulsion-based RIR-MAPLE approach has been developed that reduces substrate exposure to solvents and provides controlled and repeatable organic thin film deposition. In order to establish emulsion-based RIR-MAPLE as a preferred deposition technique for conjugated polymer or hybrid nanocomposite optoelectronic devices, studies have been conducted to demonstrate the value added by the approach in comparison to traditional solution-based deposition techniques, and this work will be reviewed. The control of hybrid nanocomposite thin film deposition, and the photoconductivity in such materials deposited using emulsion-based RIR-MAPLE, will also be reviewed. The overall result of these studies is the demonstration of emulsion-based RIR-MAPLE as a viable option for the fabrication of conjugated polymer and hybrid nanocomposite optoelectronic devices that could yield improved device performance.

  1. Fabrication of multicolor fluorescent polyvinyl alcohol through surface modification with conjugated polymers by oxidative polymerization

    Science.gov (United States)

    Hai, Thien An Phung; Sugimoto, Ryuichi

    2018-06-01

    A simple method for the preparation of multicolor polyvinyl alcohol (PVA) by chemical oxidative polymerization is introduced. The PVA surface was successfully modified with conjugated polymers composed of 3-hexylthiophene (3HT) and fluorene (F). The incorporation of the 3HT/F copolymer onto the PVA surface was confirmed by Fourier-transform infrared (FT-IR), ultraviolet-visible (UV-vis), and fluorescence spectroscopies, X-ray diffraction (XRD), as well as thermogravimetric analysis (TGA), contact angle, and field-emission scanning electron microscopy (FE-SEM) coupled with energy dispersive X-ray (EDX) analysis. Different 3HT/F ratios on the PVA surface result in optical properties that include multicolor-emission and absorption behavior. The color of the resultant (3HT/F)-g-PVA shifted from red to blue, and the quantum yield increased with increasing F content. The surface hydrophobicity of the modified PVA increased significantly through grafting with the conjugated polymers, with the water contact angle increasing by 30° compared to pristine PVA. The PVA XRD peaks were less intense following surface modification. Thermogravimetric analyses reveal that the thermal stability of the PVA decreases as a result of grafting with the 3HT/F copolymers.

  2. First-principles calculation of optical absorption spectra in conjugated polymers: Role of electron-hole interaction

    International Nuclear Information System (INIS)

    Rohlfing, Michael; Tiago, M.L.; Louie, Steven G.

    2000-01-01

    Experimental and theoretical studies have shown that excitonic effects play an important role in the optical properties of conjugated polymers. The optical absorption spectrum of trans-polyacetylene, for example, can be understood as completely dominated by the formation of exciton bound states. We review a recently developed first-principles method for computing the excitonic effects and optical spectrum, with no adjustable parameters. This theory is used to study the absorption spectrum of two conjugated polymers: trans-polyacetylene and poly-phenylene-vinylene(PPV)

  3. First-principles calculation of optical absorption spectra in conjugated polymers: Role of electron-hole interaction

    Energy Technology Data Exchange (ETDEWEB)

    Rohlfing, Michael; Tiago, M.L.; Louie, Steven G.

    2000-03-20

    Experimental and theoretical studies have shown that excitonic effects play an important role in the optical properties of conjugated polymers. The optical absorption spectrum of trans-polyacetylene, for example, can be understood as completely dominated by the formation of exciton bound states. We review a recently developed first-principles method for computing the excitonic effects and optical spectrum, with no adjustable parameters. This theory is used to study the absorption spectrum of two conjugated polymers: trans-polyacetylene and poly-phenylene-vinylene(PPV).

  4. Molecular-weight dependence of interchain polaron delocalization and exciton bandwidth in high-mobility conjugated polymers

    DEFF Research Database (Denmark)

    Chang, J.F.; Clark, J.; Zhao, N.

    2006-01-01

    delocalization with increasing conjugation length and crystalline quality. From comparative studies of field-effect transistor characteristics, film morphology, and optical properties our study provides a microscopic understanding of the factors which limit the charge transport in P3HT to field-effect mobilities......Interchain interactions have a profound effect on the optical as well as charge transport properties of conjugated polymer thin films. In contrast to oligomeric model systems in solution-deposited polymer thin films the study of such effects is complicated by the complex microstructure. We present...

  5. Stabilization of Resveratrol in Blood Circulation by Conjugation to mPEG and mPEG-PLA Polymers: Investigation of Conjugate Linker and Polymer Composition on Stability, Metabolism, Antioxidant Activity and Pharmacokinetic Profile

    Science.gov (United States)

    Siddalingappa, Basavaraj; Benson, Heather A. E.; Brown, David H.; Batty, Kevin T.; Chen, Yan

    2015-01-01

    Resveratrol is naturally occurring phytochemical with diverse biological activities such as chemoprevention, anti-inflammatory, anti-cancer, anti-oxidant. But undergoes rapid metabolism in the body (half life 0.13h). Hence Polymer conjugation utilizing different chemical linkers and polymer compositions was investigated for enhanced pharmacokinetic profile of resveratrol. Ester conjugates such as α-methoxy-ω-carboxylic acid poly(ethylene glycol) succinylamide resveratrol (MeO-PEGN-Succ-RSV) (2 and 20 kDa); MeO-PEG succinyl ester resveratrol (MeO-PEGO-Succ-RSV) (2 kDa); α-methoxy poly(ethylene glycol)-co-polylactide succinyl ester resveratrol (MeO-PEG-PLAO-Succ-RSV) (2 and 6.6kDa) were prepared by carbodiimide coupling reactions. Resveratrol-PEG ethers (2 and 5 kDa) were synthesized by alkali-mediated etherification. All polymer conjugates were fully characterized in vitro and the pharmacokinetic profile of selected conjugates was characterized in rats. Buffer and plasma stability of conjugates was dependent on polymer hydrophobicity, aggregation behavior and PEG corona, with MeO-PEG-PLAO-Succ-RSV (2 kDa) showing a 3h half-life in rat plasma in vitro. Polymer conjugates irrespective of linker chemistry protected resveratrol against metabolism in vitro. MeO-PEG-PLAO-Succ-RSV (2 kDa), Resveratrol-PEG ether (2 and 5 kDa) displayed improved pharmacokinetic profiles with significantly higher plasma area under curve (AUC), slower clearance and smaller volume of distribution, compared to resveratrol. PMID:25799413

  6. Polarized Emission from Conjugated Polymer Chains Aligned by Epitaxial Growth during Off-Center Spin-Coating

    Directory of Open Access Journals (Sweden)

    Takuya Anzai

    2017-01-01

    Full Text Available Due to their macromolecular nature, conjugated polymers can be relatively easily aligned by applying a variety of processes resulting in either elongation or ordering of their conjugated backbones. Processes that induce chain alignment include electrospinning, mechanical rubbing, epitaxial growth, and nanoconfinement and unidirectional deposition techniques such as off-center spin-coating. In this study, we compare these deposition techniques by applying them to a green-emitting conjugated polymer material that exhibits liquid crystalline phase behavior. Our study reveals that while methods such as electrospinning and mechanical rubbing can be useful to locally generate polymer chain alignment, the combination of epitaxial growth using 1,3,5-trichlorobenzene as crystallizing agent with off-center spin-coating results in the formation of anisotropic nanofiber-like structures with enhanced crystallinity degree and polarized light-emission properties. The unidirectional epitaxial growth was also applied to a red-emitting polymer that exhibits polarization ratios up to 4.1. Our results emphasize that this simple solution formulation and process can be used for the fabrication of polarized thin films of a variety of conjugated polymers with potential applications in the advanced display technologies or analytical equipment fields.

  7. Interplay of alternative conjugated pathways and steric interactions on the electronic and optical properties of donor-acceptor conjugated polymers

    KAUST Repository

    Lima, Igo T.; Risko, Chad; Aziz, Saadullah Gary; Da Silva Filho, Demé trio A Da Silva; Bredas, Jean-Luc

    2014-01-01

    Donor-acceptor π-conjugated copolymers are of interest for a wide range of electronic applications, including field-effect transistors and solar cells. Here, we present a density functional theory (DFT) study of the impact of varying the conjugation pathway on the geometric, electronic, and optical properties of donor-acceptor systems. We consider both linear ("in series"), traditional conjugation among the donor-acceptor moieties versus structures where the acceptor units are appended orthogonally to the linear, donor-only conjugated backbone. Long-range-corrected hybrid functionals are used in the investigation with the values of the tuned long-range separation parameters providing an estimate of the extent of conjugation as a function of the oligomer architecture. Considerable differences in the electronic and optical properties are determined as a function of the nature of the conjugation pathway, features that should be taken into account in the design of donor-acceptor copolymers.

  8. A salt water battery with high stability and charging rates made from solution processed conjugated polymers with polar side chains

    KAUST Repository

    Moia, Davide; Giovannitti, Alexander; Szumska, Anna A.; Schnurr, Martin; Rezasoltani, Elham; Maria, Iuliana P.; Barnes, Piers R. F.; McCulloch, Iain; Nelson, Jenny

    2017-01-01

    conjugated polymer backbones, allowed the films to maintain constant capacity at high charge and discharge rates (>1000 C-rate). The electrodes also show good stability during electrochemical cycling (less than 30% decrease in capacity over >1000 cycles) and an output voltage up to 1.4 V. The performance of these semiconducting polymers with polar side-chains demonstrates the potential of this material class for fast-charging, water based electrochemical energy storage devices.

  9. Encapsulation of Polythiophene by Glycopolymer for Water Soluble Nano-wire

    Energy Technology Data Exchange (ETDEWEB)

    T Fukuda; Y Inoue; T Koga; M Matsuoka; Y Miura

    2011-12-31

    A water-soluble polythiophene (PT) was prepared by the self-assembling complex with a glycopolymer. The glycopolymer of poly(N-p-vinylbenzyl-D-lactonamide) (PVLA) formed self-assembling cylindrical structure based on the amphiphilicity even after the complexation with PT. We confirmed the improved optical functionality of PT due to the longer conjugated {pi}-orbital. It suggested that PT behaved like molecular nanowire with the self-assembled structure in the hydrophobic core of PVLA. PVLA-PT also showed specific biorecognition against corresponding lectin. These results suggested that the bioactive nanowire formation of PT with the glycopolymer was developed.

  10. Solvent-dependent self-assembly and ordering in slow-drying semi-crystalline conjugated polymer solutions

    KAUST Repository

    Zhao, Kui

    2015-09-07

    The mechanistic understanding of the intrinsic molecular self-assembly of conjugated polymers is of immense importance to controlling the microstructure development in organic semiconducting thin films, with meaningful impact on charge transport and optoelectronic properties. Yet, to date the vast majority of studies have focused on the fast solution process itself, with studies of slower intrinsic molecular self-assembly in formulations lagging behind. Here we have investigated molecular self-assembly during spontaneous organization and uncovered how changes in formulation influence the microstructure, morphology and transport properties of conjugated polymer thin films. Our results suggest that the polymer-solvent interaction is the key factor for the molecular self-assembly and changes in macroscopic charge transport, which is in contrast with most solution processes, such as spin-coating and blade coating, where solvent drying kinetics dominates the aggregation and crystallization processes. Energetically favourable interactions between the polymer and its solvent are shown to cause chain expansion, resulting in a large hydrodynamic volume and few chain entanglements in solution. This provides molecular freedom for self-assembly and is shown to greatly enhance the local and long range order of the polymer, intra-chain backbone planarity and crystallite size. These improvements, in turn, are shown to endow the conjugated polymer with high carrier transport, as demonstrated by organic thin film transistors.

  11. Semi-metallic, strong and stretchable wet-spun conjugated polymer microfibers

    KAUST Repository

    Zhou, Jian

    2015-01-21

    A dramatic improvement in electrical conductivity is necessary to make conductive polymer fibers viable candidates in applications such as flexible electrodes, conductive textiles, and fast-response sensors and actuators. In this study, high-performance poly(3,4-ethylenedioxythiophene)/poly(styrenesulfonate) (PEDOT/PSS) conjugated polymer microfibers were fabricated via wet-spinning followed by hot-drawing. Due to the combined effects of the vertical hot-drawing process and doping/de-doping the microfibers with ethylene glycol (EG), we achieved a record electrical conductivity of 2804 S cm−1. This is, to the best of our knowledge, a six-fold improvement over the best previously reported value for PEDOT/PSS fibers (467 S cm−1) and a two-fold improvement over the best values for conductive polymer films treated by EG de-doping (1418 S cm−1). Moreover, we found that these highly conductive fibers experience a semiconductor–metal transition at 313 K. They also have superior mechanical properties with a Young\\'s modulus up to 8.3 GPa, a tensile strength reaching 409.8 MPa and a large elongation before failure (21%). The most conductive fiber also demonstrates an extraordinary electrical performance during stretching/unstretching: the conductivity increased by 25% before the fiber rupture point with a maximum strain up to 21%. Simple fabrication of the semi-metallic, strong and stretchable wet-spun PEDOT/PSS microfibers described here could make them available for conductive smart electronics.

  12. Effect of interchain coupling on the excited polaron in conjugated polymers

    International Nuclear Information System (INIS)

    Li, Xiao-xue; Chen, Gang

    2017-01-01

    Based on the one-dimensional extended Su–Schrieffer–Heeger model, we theoretically investigate the effect of interchain coupling on the formation and polarization of the single-excited state of polaron in conjugated polymers. It is found that there exists a turnover value of the coupling strength, over which the excited polaron could not be formed in either of the two coupled chains. Instead, a polaron-like particle is localized at the center of each chain. In addition, we also find that the reverse polarization of the excited polaron could be enhanced for some cases in polymer when the interchain coupling becomes strong until it exceeds the critical value. - Highlights: • Effect of interchain coupling on the single-excited state of polaron is studied. • When coupling strength exceeds critical value, the excited polaron is dissociated. • Soliton pair could be dissociated into polaron-like particle with strong coupling. • Reverse polarization of excited polaron is enhanced by weak interchain coupling. • Reverse polarization is obtained more easily in solid film of polymer molecules.

  13. Effect of interchain coupling on the excited polaron in conjugated polymers

    Energy Technology Data Exchange (ETDEWEB)

    Li, Xiao-xue, E-mail: sps_lixx@ujn.edu.cn; Chen, Gang, E-mail: ss_cheng@ujn.edu.cn

    2017-02-05

    Based on the one-dimensional extended Su–Schrieffer–Heeger model, we theoretically investigate the effect of interchain coupling on the formation and polarization of the single-excited state of polaron in conjugated polymers. It is found that there exists a turnover value of the coupling strength, over which the excited polaron could not be formed in either of the two coupled chains. Instead, a polaron-like particle is localized at the center of each chain. In addition, we also find that the reverse polarization of the excited polaron could be enhanced for some cases in polymer when the interchain coupling becomes strong until it exceeds the critical value. - Highlights: • Effect of interchain coupling on the single-excited state of polaron is studied. • When coupling strength exceeds critical value, the excited polaron is dissociated. • Soliton pair could be dissociated into polaron-like particle with strong coupling. • Reverse polarization of excited polaron is enhanced by weak interchain coupling. • Reverse polarization is obtained more easily in solid film of polymer molecules.

  14. Distinct Interfacial Fluorescence in Oil-in-Water Emulsions via Exciton Migration of Conjugated Polymers.

    Science.gov (United States)

    Koo, Byungjin; Swager, Timothy M

    2017-09-01

    Commercial dyes are extensively utilized to stain specific phases for the visualization applications in emulsions and bioimaging. In general, dyes emit only one specific fluorescence signal and thus, in order to stain various phases and/or interfaces, one needs to incorporate multiple dyes and carefully consider their compatibility to avoid undesirable interactions with each other and with the components in the system. Herein, surfactant-type, perylene-endcapped fluorescent conjugated polymers that exhibit two different emissions are reported, which are cyan in water and red at oil-water interfaces. The interfacially distinct red emission results from enhanced exciton migration from the higher-bandgap polymer backbone to the lower-bandgap perylene endgroup. The confocal microscopy images exhibit the localized red emission exclusively from the circumference of oil droplets. This exciton migration and dual fluorescence of the polymers in different physical environments can provide a new concept of visualization methods in many amphiphilic colloidal systems and bioimaging. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. Effects of polarons on static polarizabilities and second order hyperpolarizabilities of conjugated polymers

    International Nuclear Information System (INIS)

    Wang Ya-Dong; Meng Yan; Di Bing; Wang Shu-Ling; An Zhong

    2010-01-01

    According to the one-dimensional tight-binding Su—Schrieffer—Heeger model, we have investigated the effects of charged polarons on the static polarizability, α xx , and the second order hyperpolarizabilities, γ xxxx , of conjugated polymers. Our results are consistent qualitatively with previous ab initio and semi-empirical calculations. The origin of the universal growth is discussed using a local-view formalism that is based on the local atomic charge derivatives. Furthermore, combining the Su-Schrieffer-Heeger model and the extended Hubbard model, we have investigated systematically the effects of electron-electron interactions on α xx and γ xxxx of charged polymer chains. For a fixed value of the nearest-neighbour interaction V, the values of α xx and γ xxxx increase as the on-site Coulomb interaction U increases for U c and decrease with U for U > U c , where U c is a critical value of U at which the static polarizability or the second order hyperpolarizability reaches a maximal value of α max or γ max . It is found that the effect of the e-e interaction on the value of α xx is dependent on the ratio between U and V for either a short or a long charged polymer. Whereas, that effect on the value of γ xxxx is sensitive both to the ratio of U to V and to the size of the molecule. (rapid communication)

  16. Impact of the Enhanced Permeability and Retention (EPR Effect and Cathepsins Levels on the Activity of Polymer-Drug Conjugates

    Directory of Open Access Journals (Sweden)

    Amit K. Rajora

    2014-08-01

    Full Text Available Polymer-drug conjugates have demonstrated clinical potential in the context of anticancer therapy. However, such promising results have, to date, failed to translate into a marketed product. Polymer-drug conjugates rely on two factors for activity: (i the presence of a defective vasculature, for passive accumulation of this technology into the tumour tissue (enhanced permeability and retention (EPR effect and (ii the presence of a specific trigger at the tumour site, for selective drug release (e.g., the enzyme cathepsin B. Here, we retrospectively analyse literature data to investigate which tumour types have proved more responsive to polymer-drug conjugates and to determine correlations between the magnitude of the EPR effect and/or expression of cathepsin B. Lung, breast and ovarian cancers showed the highest response rate (30%, 47% and 41%, respectively for cathepsin-activated conjugates and 31%, 43%, 40%, across all conjugates. An analysis of literature data on cathepsin content in various tumour types showed that these tumour types had high cathepsin content (up to 3835 ng/mg for lung cancer, although marked heterogeneity was observed across different studies. In addition, these tumour types were also reported as having a high EPR effect. Our results suggest that a pre-screening of patient population could bring a more marked clinical benefit.

  17. Enhanced visible-light photocatalysis and gas sensor properties of polythiophene supported tin doped titanium nanocomposite

    Science.gov (United States)

    Chandra, M. Ravi; Siva Prasada Reddy, P.; Rao, T. Siva; Pammi, S. V. N.; Siva Kumar, K.; Vijay Babu, K.; Kiran Kumar, Ch.; Hemalatha, K. P. J.

    2017-06-01

    The polythiophene supported tin doped titanium nanocomposites (PTh/Sn-TiO2) were synthesized by modified sol-gel process through oxidative polymerization of thiophene. The fourier transform infrared spectroscopy (FT-IR) and UV-Vis diffuse reflectance spectroscopy (UV-DRS) analysis confirms the existence of synergetic interaction between metal oxide and polymer along with extension of absorption edge to visible region. The composites are found to be in spherical form with core-shell structure, which is confirmed by scanning electron spectroscopy (SEM) and transmission electron microscopy (TEM) images, the presence of all respective elements of composite are proven by energy-dispersive X-ray spectroscopy (EDX) analysis. The importance of polythiophene on surface of metal oxide has been were studied as a function of photocatalytic activity for degradation of organic pollutant congo red and gas sensor behavior towards liquid petroleum gas (LPG). All the composites are photocatalytically active and the composite with 1.5 wt% thiophene degrades the pollutant congo red within 120 min when compared to remaining catalysts under visible light irradiation. On the other hand, same composite have shown potential gas sensor properties towards LPG at 300 °C. Considering all the results, it can be noted that polythiophene acts as good sensitizer towards LPG and supporter for the tin doped titania that improve the photocatalytic activity under visible light.

  18. Immunoglobulin and enzyme-conjugated dextran polymers enhance u-PAR staining intensity of carcinoma cells in peripheral blood smears

    DEFF Research Database (Denmark)

    Werther, K; Normark, M; Hansen, B F

    1999-01-01

    phenotyping of disseminated carcinoma cells in bone marrow and peripheral blood smears. In the first step, the cells were incubated with antibodies against urokinase plasminogen activator receptor (u-PAR) and subsequently with secondary antibodies conjugated to peroxidase-labeled dextran polymers. A brown...

  19. Charge carrier mobility, photovoltaic, and electroluminescent properties of anthracene-based conjugated polymers bearing randomly distributed side chains

    Czech Academy of Sciences Publication Activity Database

    Usluer, Ö.; Kästner, C.; Abbas, M.; Ulbricht, C.; Cimrová, Věra; Wild, A.; Birckner, E.; Tekin, N.; Sariciftci, N. S.; Hoppe, H.; Rathgeber, S.; Egbe, D. A. M.

    2012-01-01

    Roč. 50, č. 16 (2012), s. 3425-3436 ISSN 0887-624X R&D Projects: GA MŠk(CZ) 1M06031 Institutional research plan: CEZ:AV0Z40500505 Keywords : conjugated polymers * organic field-effect transistors * organic solar cells Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 3.543, year: 2012

  20. Siloxane-Terminated Solubilizing Side Chains: Bringing Conjugated Polymer Backbones Closer and Boosting Hole Mobilities in Thin-Film Transistors

    KAUST Repository

    Mei, Jianguo; Kim, Do Hwan; Ayzner, Alexander L.; Toney, Michael F.; Bao, Zhenan

    2011-01-01

    We introduce a novel siloxane-terminated solubilizing group and demonstrate its effectiveness as a side chain in an isoindigo-based conjugated polymer. An average hole mobility of 2.00 cm 2 V -1 s -1 (with a maximum mobility of 2.48 cm 2 V -1 s -1

  1. Transient photoconductivity and femtosecond nonlinear optical properties of a conjugated polymer-graphene oxide composite

    Energy Technology Data Exchange (ETDEWEB)

    Nalla, Venkatram; Ji Wei [Department of Physics, National University of Singapore, Singapore 117542 (Singapore); Polavarapu, Lakshminarayana; Manga, Kiran Kumar; Goh, Bee Min; Loh, Kian Ping; Xu Qinghua, E-mail: chmxqh@nus.edu.sg, E-mail: phyjiwei@nus.edu.sg [Department of Chemistry, National University of Singapore, Singapore 117543 (Singapore)

    2010-10-15

    A water soluble conjugated thiophene polymer, sodium salt of poly[2-(3-thienyl)ethoxy-4-butylsulfonate] (TPP), and graphene oxide (GO) composite film (GO-TPP) device was prepared. Transient photoconductivity measurements were carried out on the GO-TPP composite film using 150 ns laser pulses of 527 nm wavelength. Highly efficient photocurrent generation was observed from the GO-TPP film. The relationships of the film photoconductivity, photocurrent decay time and electron decay times with the incident light intensity were investigated. The photoconductive gain of the film was determined to be greater than 40% and to be independent of the light intensity. Furthermore, the femtosecond nonlinear optical properties of the GO-TPP film were measured using 800 nm femtosecond laser pulses and the composite film exhibited high nonlinear absorption and nonlinear refraction coefficients.

  2. Interactions of a zwitterionic thiophene-based conjugated polymer with surfactants

    DEFF Research Database (Denmark)

    Costa, Telma; De Azevedo, Diego; Stewart, Beverly

    2015-01-01

    In this paper we investigate the optical and structural properties of a zwitterionic poly[3-(N-(4-sulfonato-1-butyl)-N,N-diethylammonium)hexyl-2,5-thiophene] (P3SBDEAHT) conjugated polyelectrolyte (CPE) and its interaction in water with surfactants, using absorption, photoluminescence (PL......), electrical conductivity, molecular dynamics simulations (MDS) and small-angle X-ray scattering (SAXS). Different surfactants were studied to evaluate the effect of the head group and chain length on the self-assembly. PL data emphasize the importance of polymer-surfactant electrostatic interactions...... in the formation of complexes. Nevertheless, conductivity and MDS data have shown that nonspecific interactions also play an important role. These seem to be responsible for the spatial position of the surfactant tail in the complex and, eventually, for breaking-up P3SBDEAHT aggregates. SAXS measurements on P3...

  3. Thiophene fused azacoronenes: regioselective synthesis, self organization, charge transport, and its incorporation in conjugated polymers

    Science.gov (United States)

    Liu, Yi; He, Bo

    2015-09-15

    A regioselective synthesis of an azacoronene fused with two peripheral thiophene groups has been realized through a concise synthetic route. The resulting thienoazacoronene (TAC) derivatives show high degree of self-organization in solution, in single crystals, in the bulk, and in spuncast thin films. Spuncast thin film field-effect transistors of the TACs exhibited mobilities up to 0.028 cm.sup.2V.sup.-1 S.sup.-1, which is among the top field effect mobilities for solution processed discotic materials. Organic photovoltaic devices using TAC-containing conjugated polymers as the donor material exhibited a high open-circuit voltage of 0.89 V, which was ascribable to TAC's low-lying highest occupied molecular orbital energy level.

  4. Transient photoconductivity and femtosecond nonlinear optical properties of a conjugated polymer-graphene oxide composite

    International Nuclear Information System (INIS)

    Nalla, Venkatram; Ji Wei; Polavarapu, Lakshminarayana; Manga, Kiran Kumar; Goh, Bee Min; Loh, Kian Ping; Xu Qinghua

    2010-01-01

    A water soluble conjugated thiophene polymer, sodium salt of poly[2-(3-thienyl)ethoxy-4-butylsulfonate] (TPP), and graphene oxide (GO) composite film (GO-TPP) device was prepared. Transient photoconductivity measurements were carried out on the GO-TPP composite film using 150 ns laser pulses of 527 nm wavelength. Highly efficient photocurrent generation was observed from the GO-TPP film. The relationships of the film photoconductivity, photocurrent decay time and electron decay times with the incident light intensity were investigated. The photoconductive gain of the film was determined to be greater than 40% and to be independent of the light intensity. Furthermore, the femtosecond nonlinear optical properties of the GO-TPP film were measured using 800 nm femtosecond laser pulses and the composite film exhibited high nonlinear absorption and nonlinear refraction coefficients.

  5. Real-time detection of metal ions using conjugated polymer composite papers.

    Science.gov (United States)

    Lee, Ji Eun; Shim, Hyeon Woo; Kwon, Oh Seok; Huh, Yang-Il; Yoon, Hyeonseok

    2014-09-21

    Cellulose, a natural polymeric material, has widespread technical applications because of its inherent structural rigidity and high surface area. As a conjugated polymer, polypyrrole shows practical potential for a diverse and promising range of future technologies. Here, we demonstrate a strategy for the real-time detection and removal of metal ions with polypyrrole/cellulose (PPCL) composite papers in solution. Simply, the conjugated polymer papers had different chemical/physical properties by applying different potentials to them, which resulted in differentiable response patterns and adsorption efficiencies for individual metal ions. First, large-area PPCL papers with a diameter of 5 cm were readily obtained via vapor deposition polymerization. The papers exhibited both mechanical flexibility and robustness, in which polypyrrole retained its redox property perfectly. The ability of the PPCL papers to recognize metal ions was examined in static and flow cells, in which real-time current change was monitored at five different applied potentials (+1, +0.5, 0, -0.5, and -1 V vs. Ag/AgCl). Distinguishable signals in the PPCL paper responses were observed for individual metal ions through principal component analysis. Particularly, the PPCL papers yielded unique signatures for three metal ions, Hg(ii), Ag(i), and Cr(iii), even in a real sample, groundwater. The sorption of metal ions by PPCL papers was examined in the flow system. The PPCL papers had a greatly superior adsorption efficiency for Hg(ii) compared to that of the other metal ions. With the strong demand for the development of inexpensive, flexible, light-weight, and environmentally friendly devices, the fascinating characteristics of these PPCL papers are likely to provide good opportunities for low-cost paper-based flexible or wearable devices.

  6. Smart conjugated polymer nanocarrier for healthy weight loss by negative feedback regulation of lipase activity

    Science.gov (United States)

    Chen, Yu-Lei; Zhu, Sha; Zhang, Lei; Feng, Pei-Jian; Yao, Xi-Kuang; Qian, Cheng-Gen; Zhang, Can; Jiang, Xi-Qun; Shen, Qun-Dong

    2016-02-01

    Healthy weight loss represents a real challenge when obesity is increasing in prevalence. Herein, we report a conjugated polymer nanocarrier for smart deactivation of lipase and thus balancing calorie intake. After oral administration, the nanocarrier is sensitive to lipase in the digestive tract and releases orlistat, which deactivates the enzyme and inhibits fat digestion. It also creates negative feedback to control the release of itself. The nanocarrier smartly regulates activity of the lipase cyclically varied between high and low levels. In spite of high fat diet intervention, obese mice receiving a single dose of the nanocarrier lose weight over eight days, whereas a control group continues the tendency to gain weight. Daily intragastric administration of the nanocarrier leads to lower weight of livers or fat pads, smaller adipocyte size, and lower total cholesterol level than that of the control group. Near-infrared fluorescence of the nanocarrier reveals its biodistribution.Healthy weight loss represents a real challenge when obesity is increasing in prevalence. Herein, we report a conjugated polymer nanocarrier for smart deactivation of lipase and thus balancing calorie intake. After oral administration, the nanocarrier is sensitive to lipase in the digestive tract and releases orlistat, which deactivates the enzyme and inhibits fat digestion. It also creates negative feedback to control the release of itself. The nanocarrier smartly regulates activity of the lipase cyclically varied between high and low levels. In spite of high fat diet intervention, obese mice receiving a single dose of the nanocarrier lose weight over eight days, whereas a control group continues the tendency to gain weight. Daily intragastric administration of the nanocarrier leads to lower weight of livers or fat pads, smaller adipocyte size, and lower total cholesterol level than that of the control group. Near-infrared fluorescence of the nanocarrier reveals its biodistribution

  7. Effect of temperature and ph on the drug release rate from a polymer conjugate system

    International Nuclear Information System (INIS)

    Kenawy, E.; Abdel-Hay, F.I.; El-Newehy, M.H.; Ottenbrite, R.M.

    2005-01-01

    Hydroximide and A-methylhydroxamic acid of poly(ethylene-altmaleic anhydride) (average MW 100-500 k) were used as a carrier for a new drug delivery system. The synthesis of the hydroximide and N methylhydroxamic acid of poly(ethylene-alt-maleic anhydride) were carried out by chemical modification of poly(ethylene-alt-maleic anhydride) with hydroxylamine and N-methyl hydroxylamine, respectively, in N,N- dimethylformamide at room temperature to yield water soluble copolymer. Ketoprofen was reacted with hydroximide and N-methylhydroxamic acid derivatives of poly(ethylene-alt-maleic anhydride) using dicyclohexylcarbodiimide as condensation agent at -5 degree C to yield water insoluble ketoprofen conjugates. All products were characterized by elemental analysis, FTIR and 1HNMR spectra. The in-vitro ketoprofen release was carried out by UV spectrophotometer at max =260 nm. The results demonstrated the effectiveness of hydroximide and N-methylhydroxamic acid of polyethylene-alt-maleic anhydride) as a drug delivery system. The release rates were studied at various ph and temperatures. The copolymer-drug adducts released the drug very slowly at the low ph found in the stomach thus protecting the drug from the action of high concentrations of digestive acids. These results showed the usefulness of hydroxamic acid polymer-drug conjugates as a new drug delivery system for drugs to be targeted to sites in the GI system

  8. Non-Fullerene Polymer Solar Cells Based on Alkylthio and Fluorine Substituted 2D-Conjugated Polymers Reach 9.5% Efficiency.

    Science.gov (United States)

    Bin, Haijun; Zhang, Zhi-Guo; Gao, Liang; Chen, Shanshan; Zhong, Lian; Xue, Lingwei; Yang, Changduk; Li, Yongfang

    2016-04-06

    Non-fullerene polymer solar cells (PSCs) with solution-processable n-type organic semiconductor (n-OS) as acceptor have seen rapid progress recently owing to the synthesis of new low bandgap n-OS, such as ITIC. To further increase power conversion efficiency (PCE) of the devices, it is of a great challenge to develop suitable polymer donor material that matches well with the low bandgap n-OS acceptors thus providing complementary absorption and nanoscaled blend morphology, as well as suppressed recombination and minimized energy loss. To address this challenge, we synthesized three medium bandgap 2D-conjugated bithienyl-benzodithiophene-alt-fluorobenzotriazole copolymers J52, J60, and J61 for the application as donor in the PSCs with low bandgap n-OS ITIC as acceptor. The three polymers were designed with branched alkyl (J52), branched alkylthio (J60), and linear alkylthio (J61) substituent on the thiophene conjugated side chain of the benzodithiophene (BDT) units for studying effect of the substituents on the photovoltaic performance of the polymers. The alkylthio side chain, red-shifted absorption down-shifted the highest occupied molecular orbital (HOMO) level and improved crystallinity of the 2D conjugated polymers. With linear alkylthio side chain, the tailored polymer J61 exhibits an enhanced JSC of 17.43 mA/cm(2), a high VOC of 0.89 V, and a PCE of 9.53% in the best non-fullerene PSCs with the polymer as donor and ITIC as acceptor. To the best of our knowledge, the PCE of 9.53% is one of the highest values reported in literature to date for the non-fullerene PSCs. The results indicate that J61 is a promising medium bandgap polymer donor in non-fullerene PSCs.

  9. Improving the in vivo therapeutic index of siRNA polymer conjugates through increasing pH responsiveness.

    Science.gov (United States)

    Guidry, Erin N; Farand, Julie; Soheili, Arash; Parish, Craig A; Kevin, Nancy J; Pipik, Brenda; Calati, Kathleen B; Ikemoto, Nori; Waldman, Jacob H; Latham, Andrew H; Howell, Bonnie J; Leone, Anthony; Garbaccio, Robert M; Barrett, Stephanie E; Parmar, Rubina Giare; Truong, Quang T; Mao, Bing; Davies, Ian W; Colletti, Steven L; Sepp-Lorenzino, Laura

    2014-02-19

    Polymer based carriers that aid in endosomal escape have proven to be efficacious siRNA delivery agents in vitro and in vivo; however, most suffer from cytotoxicity due in part to a lack of selectivity for endosomal versus cell membrane lysis. For polymer based carriers to move beyond the laboratory and into the clinic, it is critical to find carriers that are not only efficacious, but also have margins that are clinically relevant. In this paper we report three distinct categories of polymer conjugates that improve the selectivity of endosomal membrane lysis by relying on the change in pH associated with endosomal trafficking, including incorporation of low pKa heterocycles, acid cleavable amino side chains, or carboxylic acid pH sensitive charge switches. Additionally, we determine the therapeutic index of our polymer conjugates in vivo and demonstrate that the incorporation of pH responsive elements dramatically expands the therapeutic index to 10-15, beyond that of the therapeutic index (less than 3), for polymer conjugates previously reported.

  10. Synthesis and luminescent properties of new conjugated polymers based on poly(p-phenylene vinylene)

    Science.gov (United States)

    Gurge, Ronald Matthew

    The "push-pull" electronically substituted polymers poly(2 (5) -bromo-5 (2) -n-hexyloxy-1,4-phenylene vinylene), poly(2 (5) -chloro-5 (2) -n-hexyloxy-1,4-phenylene vinylene) and poly(2 (5) -fluoro-5 (2) -n-hexyloxy-1,4-phenylene vinylene) were synthesized by a soluble precursor method and were used to fabricate light emitting diode (LED) devices. Thermal elimination of the polyether precursors gives final conjugated polymers as flexible red films. Precursor polymers can be spin-cast from solutions onto indium/tin oxide (ITO) pretreated quartz plates, then thermally converted to the final red polymers. Light emitting diode fabrication is then completed by the thin film vapor deposition of calcium, followed by aluminum. LED devices of the "push-pull" polymers give light emission in the 620-635 nm range. Two fluorinated polymers, poly(2-fluoro-1,4-phenylene vinylene) and poly(2,5-difluoro-1,4-phenylene vinylene) were investigated for their electroluminescent (EL) properties. LED's using these materials as emissive layers show substantial EL wavelength shifts (560 nm and 600 nm, respectively) relative to emission from unsubstituted poly(1,4-phenylene vinylene) (565 nm). These differences in EL emission can be attributed to the electronic effects of fluorine substitution. Synthetic strategies were developed for copolymeric materials based on poly(1,4-phenylene vinylene). The alternating block copolymer, poly (1,8-octanedioxy-2,6-dimethoxy-1,4-phenylene-1,2-ethenylene-1,4-phenylene-1,2-ethenylene-1,4-phenylene-1,2-ethenylene- 3,5-dimethoxy-1,4-phenylene) was synthesized by a modified Wittig polymerization utilizing trialkyl phosphonium salts. This resulted in a regiospecific trans-olefination reaction when compared to polymeric materials synthesized through the use of common triaryl-phosphonium salts. Harsh post-Wittig isomerization procedures using Isb2 were bypassed as a result of the high trans-cis ratio of the final copolymer. It was fully characterized using the

  11. Photochemical stability of conjugated polymers, electron acceptors and blends for polymer solar cells resolved in terms of film thickness and absorbance

    DEFF Research Database (Denmark)

    Tromholt, Thomas; Vesterager Madsen, Morten; Carlé, Jon Eggert

    2012-01-01

    Photochemical degradation at 1 sun under AM1.5G illumination was performed on six conjugated polymers and five different electron acceptors. Additionally, the respective polymer:PC60BM and P3HT:electron acceptor blends were studied, and all degradations were resolved in terms of film thickness...... within each material group were found to vary for both the pure polymers and the blends. The stability ranking between the materials of the pure polymers was found to be similar to the ranking for their respective blends, implying that the photochemical stability of a pure polymer is a good measure...... of its associated blend stability. Different electron acceptors were found to stabilize P3HT decreasingly with decreasing donor–acceptor LUMO–LUMO gap. Destabilization of P3HT was observed in the case of the electron acceptor ICBA. Additionally, the decreased stabilization of P3HT by high LUMO electron...

  12. Ultrafast intersystem-crossing in platinum containing π-conjugated polymers with tunable spin-orbit coupling.

    Science.gov (United States)

    Sheng, C-X; Singh, S; Gambetta, A; Drori, T; Tong, M; Tretiak, S; Vardeny, Z V

    2013-01-01

    The development of efficient organic light-emitting diodes (OLED) and organic photovoltaic cells requires control over the dynamics of spin sensitive excitations. Embedding heavy metal atoms in π-conjugated polymer chains enhances the spin-orbit coupling (SOC), and thus facilitates intersystem crossing (ISC) from the singlet to triplet manifolds. Here we use various nonlinear optical spectroscopies such as two-photon absorption and electroabsorption in conjunction with electronic structure calculations, for studying the energies, emission bands and ultrafast dynamics of spin photoexcitations in two newly synthesized π-conjugated polymers that contain intrachain platinum (Pt) atoms separated by one (Pt-1) or three (Pt-3) organic spacer units. The controllable SOC in these polymers leads to a record ISC time of white OLEDs.

  13. Ultrafast photophysics of pi-conjugated polymers for organic light emitting diode applications

    Science.gov (United States)

    Olejnik, Ella

    In this work we used the pump-probe photomodulation (PM) spectroscopy technique to measure the transient PM spectrum and decay kinetics in various pi -- conjugated polymers (PCPs) films and blends. Using two ultrafast laser systems, we covered a broad spectral range from 0.25 -- 2.5 eV in the time domain from 200 fs to 1 ns with 150 fs time resolution. We also used continuous wave (CW) photomodulation spectroscopy, photoluminescence (PL), electro-absorption and doping-induced absorption to study the photoexcitations and other optical properties of PCPs and guest/ host blends. In particular we studied two different types of Poly(thienylenevinylene) polymer derivatives. One polymer type is the ordered regio-regular (RR) and regio-random (RRa) -- PTV in which the dark exciton, 2Ag is the lowest excited state. In these polymers the photoexcited exciton shows very fast decay kinetics due to the internal conversion to the dark exciton, which results in weak PL emission; thus these two polymers are non-luminescent. The other PTV derivative is the imide -- PTV which is more luminescent due to the proximity of 1Bu and 2Ag states, that results in longer decay kinetics and a difference between the calculated value of the QEPL (9%) and the measured one (1%). We also demonstrate transient strain spectroscopy in RR -- PTV thin films, where the ultrafast energy release associated with the exciton decay gives rise to substantial static and dynamic strains in the film that dramatically influences the film's transient PM response. We also study the photophysics of poly(dioctyloxy) phenylenevinylene polymer with different isotopes, where we substituted hydrogen (H-polymer) by deuterium (D-polymer), and 12C by 13C isotopes. From the transient decay kinetics measurements we found that the exciton recombination in DOO -- PPV consists of two processes. These are: intrinsic monomolecular, and exciton-exciton annihilation (bimolecular). In the D -- polymer, different probe frequencies of

  14. Siloxane-Terminated Solubilizing Side Chains: Bringing Conjugated Polymer Backbones Closer and Boosting Hole Mobilities in Thin-Film Transistors

    KAUST Repository

    Mei, Jianguo

    2011-12-21

    We introduce a novel siloxane-terminated solubilizing group and demonstrate its effectiveness as a side chain in an isoindigo-based conjugated polymer. An average hole mobility of 2.00 cm 2 V -1 s -1 (with a maximum mobility of 2.48 cm 2 V -1 s -1), was obtained from solution-processed thin-film transistors, one of the highest mobilities reported to date. In contrast, the reference polymer with a branched alkyl side chain gave an average hole mobility of 0.30 cm 2 V -1 s -1 and a maximum mobility of 0.57 cm 2 V -1 s -1. This is largely explained by the polymer packing: our new polymer exhibited a π-π stacking distance of 3.58 Å, while the reference polymer showed a distance of 3.76 Å. © 2011 American Chemical Society.

  15. Highly efficient inverted polymer solar cells based on a cross-linkable water-/alcohol-soluble conjugated polymer interlayer.

    Science.gov (United States)

    Zhang, Kai; Zhong, Chengmei; Liu, Shengjian; Mu, Cheng; Li, Zhengke; Yan, He; Huang, Fei; Cao, Yong

    2014-07-09

    A cross-linkable water/alcohol soluble conjugated polymer (WSCP) material poly[9,9-bis(6'-(N,N-diethylamino)propyl)-fluorene-alt-9,9-bis(3-ethyl(oxetane-3-ethyloxy)-hexyl) fluorene] (PFN-OX) was designed. The cross-linkable nature of PFN-OX is good for fabricating inverted polymer solar cells (PSCs) with well-defined interface and investigating the detailed working mechanism of high-efficiency inverted PSCs based on poly[4,8-bis(2-ethylhexyloxyl)benzo[1,2-b:4,5-b']dithio-phene-2,6-diyl-alt-ethylhexyl-3-fluorothithieno[3,4-b]thiophene-2-carboxylate-4,6-diyl] (PTB7) and (6,6)-phenyl-C71-butyric acid methyl ester (PC71BM) blend active layer. The detailed working mechanism of WSCP materials in high-efficiency PSCs were studied and can be summarized into the following three effects: a) PFN-OX tunes cathode work function to enhance open-circuit voltage (Voc); b) PFN-OX dopes PC71BM at interface to facilitate electron extraction; and c) PFN-OX extracts electrons and blocks holes to enhance fill factor (FF). On the basis of this understanding, the hole-blocking function of the PFN-OX interlayer was further improved with addition of a ZnO layer between ITO and PFN-OX, which led to inverted PSCs with a power conversion efficiency of 9.28% and fill factor high up to 74.4%.

  16. Charge transport in conjugated polymer-semiconductor nanoparticle composite near the percolation threshold

    Science.gov (United States)

    Cardoso, L. S.; Gonçalves, G. E.; Kanda, D. H. F.; Bianchi, R. F.; Nagashima, H. N.

    2017-12-01

    This paper describes a new statistical model to predict the frequency dependence of the conductivity of conjugated polymer-semiconductor nanoparticle composites. The model considers AC conduction in an inhomogeneous medium represented by a two-dimensional model of resistor network. The conductivity between two neighboring sites in the polymer matrix and the semiconductor particles is assumed to obey the random free energy barrier model and the Drude model, respectively. The real and imaginary parts of the AC conductivity were determined using the transfer-matrix technique, and the statistical model was applied to experimental data of thin films composed of polyaniline (PANI) and indium-tin-oxide (ITO) nanoparticles. The conductivity critical exponent ( s) obtained in two dimensions for PANI/ITO films below the percolation threshold was found to be 2.7, which is greater than the universal value of s described by the classical percolation theory ( s = 1.3). This non-universality is explained by the existence of a local electric field distribution in the bulk of the nanocomposite. Finally, these results are discussed in terms of the distribution of potential barriers that vary according to the concentration of ITO amount in the composite.

  17. White light generation tuned by dual hybridization of nanocrystals and conjugated polymers

    International Nuclear Information System (INIS)

    Demir, Hilmi Volkan; Nizamoglu, Sedat; Ozel, Tuncay; Mutlugun, Evren; Huyal, Ilkem Ozge; Sari, Emre; Holder, Elisabeth; Tian Nan

    2007-01-01

    Dual hybridization of highly fluorescent conjugated polymers and highly luminescent nanocrystals (NCs) is developed and demonstrated in multiple combinations for controlled white light generation with high color rendering index (CRI) (> 80) for the first time. The generated white light is tuned using layer-by-layer assembly of CdSe/ZnS core-shell NCs closely packed on polyfluorene, hybridized on near-UV emitting nitride-based light emitting diodes (LEDs). The design, synthesis, growth, fabrication and characterization of these hybrid inorganic-organic white LEDs are presented. The following experimental realizations are reported: (i) layer-by-layer hybridization of yellow NCs (λ PL =580 nm) and blue polyfluorene (λ PL =439 nm) with tristimulus coordinates of (x, y)=(0.31, 0.27), correlated color temperature of T c =6962 K and CRI of R a =53.4; (ii) layer-by-layer assembly of yellow and green NCs (λ PL =580 and 540 nm) and blue polyfluorene (λ PL =439 nm) with (x, y)=(0.23, 0.30), T c =14395 K and R a =65.7; and (iii) layer-by-layer deposition of yellow, green and red NCs (λ PL =580, 540 and 620 nm) and blue polyfluorene (λ PL =439 nm) with (x, y)=(0.38, 0.39), T c =4052 K and R a = 83.0. The CRI is demonstrated to be well controlled and significantly improved by increasing multi-chromaticity of the NC and polymer emitters

  18. Photoinduced charge and energy transfer in dye-doped conjugated polymers

    International Nuclear Information System (INIS)

    Veldman, Dirk; Bastiaansen, Jolanda J.A.M.; Langeveld-Voss, Bea M.W.; Sweelssen, Joergen; Koetse, Marc M.; Meskers, Stefan C.J.; Janssen, Rene A.J.

    2006-01-01

    Conjugated polymer-molecular dye blends of MDMO-PPV (poly[2-methoxy-5-(3',7'-dimethyloctyloxy)-1,4-phenylenevinylene]) and PF1CVTP (poly[9,9-dioctylfluorene-2,7-diyl-alt-2,5-bis(2-thienyl-1-cyanovinyl) -1-(3',7= '-dimethyloctyloxy)-4-methoxybenzene-5'',5''-diyl]) with three dipyrrometheneboron difluoride (bodipy) dyes were studied by (time-resolved) fluorescence and photoinduced absorption spectroscopy to determine quantitatively the relation between the electronic HOMO and LUMO levels and the occurrence of energy or charge transfer after optical excitation. We find that for MDMO-PPV photoinduced charge transfer to the dyes occurs, while photoexcitation of PF1CVTP exclusively results in energy transfer. The differences can be rationalized by assuming that the energy of the charge separated state is 0.33-0.45 eV higher than the energy determined from oxidation and reduction potentials of donor and acceptor, respectively. This provides an important design rule to identify appropriate materials for polymer solar cells that can have a high open-circuit voltage

  19. Characterization of electrosynthesized conjugated polymer-carbon nanotube composite: optical nonlinearity and electrical property.

    Science.gov (United States)

    Bahrami, Afarin; Talib, Zainal Abidin; Shahriari, Esmaeil; Yunus, Wan Mahmood Mat; Kasim, Anuar; Behzad, Kasra

    2012-01-01

    The effects of multi-walled carbon nanotube (MWNT) concentration on the structural, optical and electrical properties of conjugated polymer-carbon nanotube composite are discussed. Multi-walled carbon nanotube-polypyrrole nanocomposites were synthesized by electrochemical polymerization of monomers in the presence of different amounts of MWNTs using sodium dodecylbenzensulfonate (SDBS) as surfactant at room temperature and normal pressure. Field emission scanning electron microscopy (FESEM) indicates that the polymer is wrapped around the nanotubes. Measurement of the nonlinear refractive indices (n(2)) and the nonlinear absorption (β) of the samples with different MWNT concentrations measurements were performed by a single Z-scan method using continuous wave (CW) laser beam excitation wavelength of λ = 532 nm. The results show that both nonlinear optical parameters increased with increasing the concentration of MWNTs. The third order nonlinear susceptibilities were also calculated and found to follow the same trend as n(2) and β. In addition, the conductivity of the composite film was found to increase rapidly with the increase in the MWNT concentration.

  20. Comparison of selenophene and thienothiophene incorporation into pentacyclic lactam-based conjugated polymers for organic solar cells

    KAUST Repository

    Kroon, Renee; Melianas, Armantas; Zhuang, Wenliu; Bergqvist, Jonas; Diaz De Zerio Mendaza, Amaia; Steckler, Timothy T.; Yu, Liyang; Bradley, Siobhan J.; Musumeci, Chiara; Gedefaw, Desta; Nann, Thomas; Amassian, Aram; Mü ller, Christian; Inganä s, Olle; Andersson, Mats R.

    2015-01-01

    In this work, we compare the effect of incorporating selenophene versus thienothiophene spacers into pentacyclic lactam-based conjugated polymers for organic solar cells. The two cyclic lactam-based copolymers were obtained via a new synthetic method for the lactam moiety. Selenophene incorporation results in a broader and red-shifted optical absorption while retaining a deep highest occupied molecular orbital level, whereas thienothienophene incorporation results in a blue-shifted optical absorption. Additionally, grazing-incidence wide angle X-ray scattering data indicates edge- and face-on solid state order for the selenophene-based polymer as compared to the thienothiophene-based polymer, which orders predominantly edge-on with respect to the substrate. In polymer:PCBM bulk heterojunction solar cells both materials show a similar open-circuit voltage of ∼0.80-0.84 V, however the selenophene-based polymer displays a higher fill factor of ∼0.70 vs. ∼0.65. This is due to the partial face-on backbone orientation of the selenophene-based polymer, leading to a higher hole mobility, as confirmed by single-carrier diode measurements, and a concomitantly higher fill factor. Combined with improved spectral coverage of the selenophene-based polymer, as confirmed by quantum efficiency experiments, it offers a larger short-circuit current density of ∼12 mA cm. Despite the relatively low molecular weight of both materials, a very robust power conversion efficiency ∼7% is achieved for the selenophene-based polymer, while the thienothiophene-based polymer demonstrates only a moderate maximum PCE of ∼5.5%. Hence, the favorable effects of selenophene incorporation on the photovoltaic performance of pentacyclic lactam-based conjugated polymers are clearly demonstrated.

  1. Comparison of selenophene and thienothiophene incorporation into pentacyclic lactam-based conjugated polymers for organic solar cells

    KAUST Repository

    Kroon, Renee

    2015-09-08

    In this work, we compare the effect of incorporating selenophene versus thienothiophene spacers into pentacyclic lactam-based conjugated polymers for organic solar cells. The two cyclic lactam-based copolymers were obtained via a new synthetic method for the lactam moiety. Selenophene incorporation results in a broader and red-shifted optical absorption while retaining a deep highest occupied molecular orbital level, whereas thienothienophene incorporation results in a blue-shifted optical absorption. Additionally, grazing-incidence wide angle X-ray scattering data indicates edge- and face-on solid state order for the selenophene-based polymer as compared to the thienothiophene-based polymer, which orders predominantly edge-on with respect to the substrate. In polymer:PCBM bulk heterojunction solar cells both materials show a similar open-circuit voltage of ∼0.80-0.84 V, however the selenophene-based polymer displays a higher fill factor of ∼0.70 vs. ∼0.65. This is due to the partial face-on backbone orientation of the selenophene-based polymer, leading to a higher hole mobility, as confirmed by single-carrier diode measurements, and a concomitantly higher fill factor. Combined with improved spectral coverage of the selenophene-based polymer, as confirmed by quantum efficiency experiments, it offers a larger short-circuit current density of ∼12 mA cm. Despite the relatively low molecular weight of both materials, a very robust power conversion efficiency ∼7% is achieved for the selenophene-based polymer, while the thienothiophene-based polymer demonstrates only a moderate maximum PCE of ∼5.5%. Hence, the favorable effects of selenophene incorporation on the photovoltaic performance of pentacyclic lactam-based conjugated polymers are clearly demonstrated.

  2. Novel bioadhesive polymers as intra-articular agents: Chondroitin sulfate-cysteine conjugates.

    Science.gov (United States)

    Suchaoin, Wongsakorn; Bonengel, Sonja; Griessinger, Julia Anita; Pereira de Sousa, Irene; Hussain, Shah; Huck, Christian W; Bernkop-Schnürch, Andreas

    2016-04-01

    The aim of this study was to generate and characterize a chondroitin sulfate-cysteine conjugate (CS-cys) as a novel bioadhesive agent for intra-articular use. Mucoadhesive properties of synthesized CS-cys were investigated by rheological measurement of polymer-mucus mixture and rotating cylinder method, while bioadhesive features of CS-cys on porcine articular cartilage were evaluated via tensile studies. Thiolation was achieved by attachment of l-cysteine to CS via amide bond formation mediated by carbodiimide as a coupling reagent. The conjugate exhibited 421.17±35.14 μmol free thiol groups per gram polymer. The reduced CS-cys displayed 675.09±39.67 μmol free thiol groups per gram polymer after disulfide bonds reduction using tris(2-carboxyethyl)phosphine hydrochloride. The increase in dynamic viscosity of thiolated CS due to oxidative disulfide bond formation was demonstrated using capillary viscometer. The combination of CS-cys and mucus led to 4.57-fold increase in dynamic viscosity in comparison with mucus control. Furthermore, adhesion time to porcine mucosa of CS-cys-based test disk was enhanced by 2.48-fold compared to unmodified CS as measured by rotating cylinder method suggesting the interaction between thiomers and mucus gel layer via disulfide bonds formation. Tensile studies of thiolated CS on porcine articular cartilage showed 5.37- and 1.76-fold increase in the total work of adhesion and the maximum detachment force, respectively, in comparison with unmodified CS indicating bioadhesive features of CS-cys. Cytotoxicity of CS-cys was assessed in Caco-2 cells and rat primary articular chondrocytes using MTT and LDH release assay, thereby showing the safety of CS-cys at a concentration of 0.25% (w/v) in Caco-2 cells. Furthermore, 0.1% of CS-cys was found non-toxic to rat primary articular chondrocytes. According to these results, CS-cys provides improved bioadhesive properties that might be useful as an intra-articular agent for treatment of

  3. Hydrophilic Conjugated Polymers with Large Bandgaps and Deep-Lying HOMO Levels as an Efficient Cathode Interlayer in Inverted Polymer Solar Cells.

    Science.gov (United States)

    Kan, Yuanyuan; Zhu, Yongxiang; Liu, Zhulin; Zhang, Lianjie; Chen, Junwu; Cao, Yong

    2015-08-01

    Two hydrophilic conjugated polymers, PmP-NOH and PmP36F-NOH, with polar diethanol-amine on the side chains and main chain structures of poly(meta-phenylene) and poly(meta-phenylene-alt-3,6-fluorene), respectively, are successfully synthesized. The films of PmP-NOH and PmP36F-NOH show absorption edges at 340 and 343 nm, respectively. The calculated optical bandgaps of the two polymers are 3.65 and 3.62 eV, respectively, the largest ones so far reported for hydrophilic conjugated polymers. PmP-NOH and PmP36F-NOH also possess deep-lying highest occupied molecular orbital levels of -6.19 and -6.15 eV, respectively. Inserting PmP-NOH and PmP36F-NOH as a cathode interlayer in inverted polymer solar cells with a PTB7/PC71 BM blend as the active layer, high power conversion efficiencies of 8.58% and 8.33%, respectively, are achieved, demonstrating that the two hydrophilic polymers are excellent interlayers for efficient inverted polymer solar cells. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  4. A Triphenylamine-Based Conjugated Polymer with Donor-π-Acceptor Architecture as Organic Sensitizer for Dye-Sensitized Solar Cells.

    Science.gov (United States)

    Zhang, Wei; Fang, Zhen; Su, Mingjuan; Saeys, Mark; Liu, Bin

    2009-09-17

    A conjugated polymer containing an electron donating backbone (triphenylamine) and an electron accepting side chain (cyanoacetic acid) with conjugated thiophene units as the linkers has been synthesized. Dye-sensitized solar cells (DSSCs) are fabricated utilizing this material as the dye sensitizer, resulting a typical power conversion efficiency of 3.39% under AM 1.5 G illumination, which represents the highest efficiency for polymer dye-sensitized DSSCs reported so far. The results show the good promise of conjugated polymers as sensitizers for DSSC applications. Copyright © 2009 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  5. Bactericidal Specificity and Resistance Profile of Poly(Quaternary Ammonium) Polymers and Protein-Poly(Quaternary Ammonium) Conjugates.

    Science.gov (United States)

    Ji, Weihang; Koepsel, Richard R; Murata, Hironobu; Zadan, Sawyer; Campbell, Alan S; Russell, Alan J

    2017-08-14

    Antibacterial polymers are potentially powerful biocides that can destroy bacteria on contact. Debate in the literature has surrounded the mechanism of action of polymeric biocides and the propensity for bacteria to develop resistance to them. There has been particular interest in whether surfaces with covalently coupled polymeric biocides have the same mechanism of action and resistance profile as similar soluble polymeric biocides. We designed and synthesized a series of poly(quaternary ammonium) polymers, with tailorable molecular structures and architectures, to engineer their antibacterial specificity and their ability to delay the development of bacterial resistance. These linear poly(quaternary ammonium) homopolymers and block copolymers, generated using atom transfer radical polymerization, had structure-dependent antibacterial specificity toward Gram positive and negative bacterial species. When single block copolymers contained two polymer segments of differing antibacterial specificity, the polymer combined the specificities of its two components. Nanoparticulate human serum albumin-poly(quaternary ammonium) conjugates of these same polymers, synthesized via "grafting from" atom transfer radical polymerization, were strongly biocidal and also exhibited a marked decrease in the rate of bacterial resistance development relative to linear polymers. These protein-biocide conjugates mimicked the behavior of surface-presented polycationic biocides rather than their nonproteinaceous counterparts.

  6. Development and validation of an in vitro pharmacokinetic/pharmacodynamic model to test the antibacterial efficacy of antibiotic polymer conjugates.

    Science.gov (United States)

    Azzopardi, Ernest A; Ferguson, Elaine L; Thomas, David W

    2015-04-01

    This study describes the use of a novel, two-compartment, static dialysis bag model to study the release, diffusion, and antibacterial activity of a novel, bioresponsive dextrin-colistin polymer conjugate against multidrug resistant (MDR) wild-type Acinetobacter baumannii. In this model, colistin sulfate, at its MIC, produced a rapid and extensive drop in viable bacterial counts (growth for up to 48 h, with 3 log10 CFU/ml lower bacterial counts after 48 h than those of controls. Doubling the concentration of dextrin-colistin conjugate (to 2× MIC) led to an initial bacterial killing of 3 log10 CFU/ml at 8 h, with a similar regrowth profile to 1× MIC treatment thereafter. The addition of colistin sulfate (1× MIC) to dextrin-colistin conjugate (1× MIC) resulted in undetectable bacterial counts after 4 h, followed by suppressed bacterial growth (3.5 log10 CFU/ml lower than that of control at 48 h). Incubation of dextrin-colistin conjugates with infected wound exudate from a series of burn patients (n = 6) revealed an increasing concentration of unmasked colistin in the outer compartment (OC) over time (up to 86.3% of the initial dose at 48 h), confirming that colistin would be liberated from the conjugate by endogenous α-amylase within the wound environment. These studies confirm the utility of this model system to simulate the pharmacokinetics of colistin formation in humans administered dextrin-colistin conjugates and further supports the development of antibiotic polymer conjugates in the treatment of MDR infections. Copyright © 2015, American Society for Microbiology. All Rights Reserved.

  7. The optical and electrical properties of graphene oxide with water-soluble conjugated polymer composites by radiation.

    Science.gov (United States)

    Jungo, Seung Tae; Oh, Seung-Hwan; Kim, Hyun Bin; Jeun, Joon-Pyo; Lee, Bum-Jae; Kang, Phil-Hyun

    2013-11-01

    In order to overcome the difficulty of dispersion and low conductivity in composite containing graphene, graphene oxide (GO) has been used instead of neat graphene. And the GO treated by radiation, could give improved conductivity of the GO-containing polymer composite. In this study, fluorene based water-soluble conjugated polymer (WPF-6-oxy-F) was introduced in GO solution to investigate the change of optical and electrical properties through radiation process. UV-Vis absorption of irradiated WPF-6-oxy-F-GO composite was red shifted and I(D)/I(G) ratio of Raman spectra decreased. XPS analysis showed that C-N bonds was formed after the irradiation and confirmed the increased bonds between the GO and the water-soluble conjugated polymer matrix. From the AFM and XPS analysis, it was found that the water-soluble conjugated polymer matrix was stacked between the modified GO in the morphology of irradiated WPF-6-oxy-F-GO composite was increased after gamma ray irradiation up to 10(-2) S/cm.

  8. Excited State Assignment and Laser Action in π-Conjugated Polymers

    Science.gov (United States)

    Vardeny, Z. V.

    1998-03-01

    We have applied a variety of ps transient and cw spectroscopies to elucidate the ground and excited electronic states of luminescent and nonluminescent thin films and solutions of π-conjugated polymers. These techniques include photoinduced absorption (PA), photoluminescence (PL), resonant Raman scattering (RRS), electro-absorption (EA), two photon absorption (TPA), and PA detected magnetic resonance. We found that the luminescence efficiency, the resonant and subgap third-order nonlinear optical properties and the RRS dispersion in these polymers are determined by the energies and symmetries of a subset of the excited states, including a series of singlet excitons with odd (B_u) and even (A_g) parity lying below a continuum band. Among them, the lowest Bu exciton (1B_u) and two other dominant Ag excitons (mAg and kA_g) are particularly important in determining the EA, TPA, and excitonic ps PA spectra.(S.V. Frolov, M. Liess, P.A. Lane, W. Gellermann, Z.V. Vardeny, M. Ozaki, and K. Yoshino, Phys. Rev. Lett). 78, 4285 (1997). We also found(M. Ozaki, E. Ehrenfreund, R.E. Benner, T.J. Baron, K. Yoshino, and Z.V. Vardeny, Phys. Rev. Lett). 79, 1762 (1997). that the RRS phonon dispersion with the laser excitation energy is governed by the dependence of lowest Ag exciton (2A_g) on the chain length distribution in the polymer. This leads to stronger RRS dispersion in nonluminescent polymers. Moreover the relative energies of the 1Bu and 2Ag excitons determine the PL quantum efficiency η, regardless of the ground state degeneracy. If E(2A_g) < E(1B_u) then η is small because of the dipole forbidden character of the lowest singlet. We will give examples of nonluminescent polymers which belong to this class with both degenerate and nondegenerate ground state, respectively. On the other hand, if E(1B_u) < E(2A_g) then η is large and the polymer might be considered as active material for display applications. Again we give examples of highly luminescent polymers with

  9. Bis(thienothiophenyl) diketopyrrolopyrrole-based conjugated polymers with various branched alkyl side chains and their applications in thin-film transistors and polymer solar cells.

    Science.gov (United States)

    Shin, Jicheol; Park, Gi Eun; Lee, Dae Hee; Um, Hyun Ah; Lee, Tae Wan; Cho, Min Ju; Choi, Dong Hoon

    2015-02-11

    New thienothiophene-flanked diketopyrrolopyrrole and thiophene-containing π-extended conjugated polymers with various branched alkyl side-chains were successfully synthesized. 2-Octyldodecyl, 2-decyltetradecyl, 2-tetradecylhexadecyl, 2-hexadecyloctadecyl, and 2-octadecyldocosyl groups were selected as the side-chain moieties and were anchored to the N-positions of the thienothiophene-flanked diketopyrrolopyrrole unit. All five polymers were found to be soluble owing to the bulkiness of the side chains. The thin-film transistor based on the 2-tetradecylhexadecyl-substituted polymer showed the highest hole mobility of 1.92 cm2 V(-1) s(-1) due to it having the smallest π-π stacking distance between the polymer chains, which was determined by grazing incidence X-ray diffraction. Bulk heterojunction polymer solar cells incorporating [6,6]-phenyl-C71-butyric acid methyl ester as the n-type molecule and the additive 1,8-diiodooctane (1 vol %) were also constructed from the synthesized polymers without thermal annealing; the device containing the 2-octyldodecyl-substituted polymer exhibited the highest power conversion efficiency of 5.8%. Although all the polymers showed similar physical properties, their device performance was clearly influenced by the sizes of the branched alkyl side-chain groups.

  10. Entanglement of conjugated polymer chains influences molecular self-assembly and carrier transport

    KAUST Repository

    Zhao, Kui

    2013-06-26

    The influence of polymer entanglement on the self-assembly, molecular packing structure, and microstructure of low-Mw (lightly entangled) and high-Mw (highly entangled) poly (3-hexylthiophene) (P3HT), and the carrier transport in thin-film transistors, are investigated. The polymer chains are gradually disentangled in a marginal solvent via ultrasonication of the polymer solution, and demonstrate improved diffusivity of precursor species (coils, aggregates, and microcrystallites), enhanced nucleation and crystallization of P3HT in solution, and self-assembly of well-ordered and highly textured fibrils at the solid-liquid interface. In low-Mw P3HT, reducing chain entanglement enhances interchain and intrachain ordering, but reduces the interconnectivity of ordered domains (tie molecules) due to the presence of short chains, thus deteriorating carrier transport even in the face of improving crystallinity. Reducing chain entanglement in high-Mw P3HT solutions increases carrier mobility up to ≈20-fold, by enhancing interchain and intrachain ordering while maintaining a sufficiently large number of tie molecules between ordered domains. These results indicate that charge carrier mobility is strongly governed by the balancing of intrachain and interchain ordering, on the one hand, and interconnectivity of ordered domains, on the other hand. In high-Mw P3HT, intrachain and interchain ordering appear to be the key bottlenecks to charge transport, whereas in low-Mw P3HT, the limited interconnectivity of the ordered domains acts as the primary bottleneck to charge transport. Conjugated polymer chains of poly(3-hexylthiophene) (P3HT) are gradually disentangled in solution and trends in carrier transport mechanisms in organic thin film transistors for low- and high-molecular weight P3HT are investigated. While intrachain and interchain ordering within ordered domains are the key bottlenecks to charge transport in high-Mw P3HT films, the limited interconnectivity of ordered

  11. Entanglement of conjugated polymer chains influences molecular self-assembly and carrier transport

    KAUST Repository

    Zhao, Kui; Khan, Hadayat Ullah; Li, Ruipeng; Su, Yisong; Amassian, Aram

    2013-01-01

    The influence of polymer entanglement on the self-assembly, molecular packing structure, and microstructure of low-Mw (lightly entangled) and high-Mw (highly entangled) poly (3-hexylthiophene) (P3HT), and the carrier transport in thin-film transistors, are investigated. The polymer chains are gradually disentangled in a marginal solvent via ultrasonication of the polymer solution, and demonstrate improved diffusivity of precursor species (coils, aggregates, and microcrystallites), enhanced nucleation and crystallization of P3HT in solution, and self-assembly of well-ordered and highly textured fibrils at the solid-liquid interface. In low-Mw P3HT, reducing chain entanglement enhances interchain and intrachain ordering, but reduces the interconnectivity of ordered domains (tie molecules) due to the presence of short chains, thus deteriorating carrier transport even in the face of improving crystallinity. Reducing chain entanglement in high-Mw P3HT solutions increases carrier mobility up to ≈20-fold, by enhancing interchain and intrachain ordering while maintaining a sufficiently large number of tie molecules between ordered domains. These results indicate that charge carrier mobility is strongly governed by the balancing of intrachain and interchain ordering, on the one hand, and interconnectivity of ordered domains, on the other hand. In high-Mw P3HT, intrachain and interchain ordering appear to be the key bottlenecks to charge transport, whereas in low-Mw P3HT, the limited interconnectivity of the ordered domains acts as the primary bottleneck to charge transport. Conjugated polymer chains of poly(3-hexylthiophene) (P3HT) are gradually disentangled in solution and trends in carrier transport mechanisms in organic thin film transistors for low- and high-molecular weight P3HT are investigated. While intrachain and interchain ordering within ordered domains are the key bottlenecks to charge transport in high-Mw P3HT films, the limited interconnectivity of ordered

  12. The Organic Chemistry of Conducting Polymers

    Energy Technology Data Exchange (ETDEWEB)

    Tolbert, Laren Malcolm [Georgia Inst. of Technology, Atlanta, GA (United States)

    2014-12-01

    For the last several years, we have examined the fundamental principles of conduction in one-dimensional systems, i.e., molecular “wires”. It is, of course, widely recognized that such systems, as components of electronically conductive materials, function in a two- and three-dimensional milieu. Thus interchain hopping and grain-boundary resistivity are limiting conductivity factors in highly conductive materials, and overall conductivity is a function of through-chain and boundary hopping. We have given considerable attention to the basic principles underlying charge transport (the “rules of the game”) in two-dimensional systems by using model systems which allow direct observation of such processes, including the examination of tunneling and hopping as components of charge transfer. In related work, we have spent considerable effort on the chemistry of conjugated heteropolymers, most especially polythiophens, with the aim of using these most efficient of readily available electroactive polymers in photovoltaic devices.

  13. Effect of oligonucleic acid (ONA) backbone features on assembly of ONA-star polymer conjugates: a coarse-grained molecular simulation study.

    Science.gov (United States)

    Condon, Joshua E; Jayaraman, Arthi

    2017-10-04

    Understanding the impact of incorporating new physical and chemical features in oligomeric DNA mimics, termed generally as "oligonucleic acids" (ONAs), on their structure and thermodynamics will be beneficial in designing novel materials for a variety of applications. In this work, we conduct coarse-grained molecular simulations of ONA-star polymer conjugates with varying ONA backbone flexibility, ONA backbone charge, and number of arms in the star polymer at a constant ONA strand volume fraction to elucidate the effect of these design parameters on the thermodynamics and assembly of multi-arm ONA-star polymer conjugates. We quantify the thermo-reversible behavior of the ONA-star polymer conjugates by quantifying the hybridization of the ONA strands in the system as a function of temperature (i.e. melting curve). Additionally, we characterize the assembly of the ONA-star polymer conjugates by tracking cluster formation and percolation as a function of temperature, as well as cluster size distribution at temperatures near the assembly transition region. The key results are as follows. The melting temperature (T m ) of the ONA strands decreases upon going from a neutral to a charged ONA backbone and upon increasing flexibility of the ONA backbone. Similar behavior is seen for the assembly transition temperature (T a ) with varying ONA backbone charge and flexibility. While the number of arms in the ONA-star polymer conjugate has a negligible effect on the ONA T m in these systems, as the number of ONA-star polymer arms increase, the assembly temperature T a increases and local ordering in the assembled state improves. By understanding how factors like ONA backbone charge, backbone flexibility, and ONA-star polymer conjugate architecture impact the behavior of ONA-star polymer conjugate systems, we can better inform how the selection of ONA chemistry will influence resulting ONA-star polymer assembly.

  14. Driving High-Performance n- and p-type Organic Transistors with Carbon Nanotube/Conjugated Polymer Composite Electrodes Patterned Directly from Solution

    KAUST Repository

    Hellstrom, Sondra L.; Jin, Run Zhi; Stoltenberg, Randall M.; Bao, Zhenan

    2010-01-01

    We report patterned deposition of carbon nanotube/conjugated polymer composites from solution with high nanotube densities and excellent feature resolution. Such composites are suited for use as electrodes in high-performance transistors

  15. Geometrical relaxation of excitations in one-dimensional conjugated polymers; Giichijigen kyoeki kobunshi reiki jotai no shusa kozo kanwa

    Energy Technology Data Exchange (ETDEWEB)

    Yoshizawa, M. [Tohoku University, Sendai (Japan). Faculty of Engineering

    1995-12-15

    Large ultrafast optical nonlinearities in conjugated polymers have attracted much attention because of possible applications to nonlinear optical devices. One-dimensional systems such as conjugated polymers have localized excited states with geometrical relaxation. In this study, photoexcited states in polydiacetylene has been investigated by femtosecond Raman gain spectroscopy with 300-fs resolution. A new photoinduced Raman peak with lifetime of 1.5 ps has been observed at 1200cm{sup -1} for the first time. This peak indicates acetylene-like structure of the main chain relaxes to butatriene-like structure due to the formation of self-trapped exciting with the geometrical relaxation. The formation and decay kinetics of the Raman signals is consistent with the relaxation processes of exciting observed by femtosecond absorption spectroscopy. 8 refs., 5 figs.

  16. Electro-Optical and Electrochemical Properties of a Conjugated Polymer Prepared by the Cyclopolymerization of Diethyl Dipropargylmalonate

    Directory of Open Access Journals (Sweden)

    Yeong-Soon Gal

    2008-01-01

    Full Text Available The electro-optical and electrochemical properties of poly(diethyl dipropargylmalonate were measured and discussed. Poly(diethyl dipropargylmalonate prepared by (NBDPdCl2 catalyst was used for study. The chemical structure of poly(diethyl dipropargylmalonate was characterized by such instrumental methods as NMR (1H-, 13C-, IR, and UV-visible spectroscopies to have the conjugated cyclopolymer backbone system. The microstructure analysis of polymer revealed that this polymer have the six-membered ring moieties majorly. The photoluminescence peak of polymer was observed at 543 nm, which is corresponded to the photon energy of 2.51 eV. The cyclovoltamograms of the polymer exhibited the irreversible electrochemical behaviors between the doping and undoping peaks. It was found that the kinetics of the redox process of this conjugated cyclopolymer might be controlled by the diffusion-control process from the experiment of the oxidation current density of polymer versus the scan rate.

  17. White light generation tuned by dual hybridization of nanocrystals and conjugated polymers

    Energy Technology Data Exchange (ETDEWEB)

    Demir, Hilmi Volkan [Devices and Sensors Group and Nanotechnology Research Center, Bilkent University, Ankara 06800 (Turkey); Nizamoglu, Sedat [Devices and Sensors Group and Nanotechnology Research Center, Bilkent University, Ankara 06800 (Turkey); Ozel, Tuncay [Devices and Sensors Group and Nanotechnology Research Center, Bilkent University, Ankara 06800 (Turkey); Mutlugun, Evren [Devices and Sensors Group and Nanotechnology Research Center, Bilkent University, Ankara 06800 (Turkey); Huyal, Ilkem Ozge [Devices and Sensors Group and Nanotechnology Research Center, Bilkent University, Ankara 06800 (Turkey); Sari, Emre [Devices and Sensors Group and Nanotechnology Research Center, Bilkent University, Ankara 06800 (Turkey); Holder, Elisabeth [Functional Polymers Group and Institute of Polymer Technology, University of Wuppertal, Gaussstrasse 20, D-42097 Wuppertal (Germany); Tian Nan [Functional Polymers Group and Institute of Polymer Technology, University of Wuppertal, Gaussstrasse 20, D-42097 Wuppertal (Germany)

    2007-10-15

    Dual hybridization of highly fluorescent conjugated polymers and highly luminescent nanocrystals (NCs) is developed and demonstrated in multiple combinations for controlled white light generation with high color rendering index (CRI) (> 80) for the first time. The generated white light is tuned using layer-by-layer assembly of CdSe/ZnS core-shell NCs closely packed on polyfluorene, hybridized on near-UV emitting nitride-based light emitting diodes (LEDs). The design, synthesis, growth, fabrication and characterization of these hybrid inorganic-organic white LEDs are presented. The following experimental realizations are reported: (i) layer-by-layer hybridization of yellow NCs ({lambda}{sub PL}=580 nm) and blue polyfluorene ({lambda}{sub PL}=439 nm) with tristimulus coordinates of (x, y)=(0.31, 0.27), correlated color temperature of T{sub c}=6962 K and CRI of R{sub a}=53.4; (ii) layer-by-layer assembly of yellow and green NCs ({lambda}{sub PL}=580 and 540 nm) and blue polyfluorene ({lambda}{sub PL}=439 nm) with (x, y)=(0.23, 0.30), T{sub c}=14395 K and R{sub a}=65.7; and (iii) layer-by-layer deposition of yellow, green and red NCs ({lambda}{sub PL}=580, 540 and 620 nm) and blue polyfluorene ({lambda}{sub PL}=439 nm) with (x, y)=(0.38, 0.39), T{sub c}=4052 K and R{sub a}= 83.0. The CRI is demonstrated to be well controlled and significantly improved by increasing multi-chromaticity of the NC and polymer emitters.

  18. Surface chemistry of photoluminescent F8BT conjugated polymer nanoparticles determines protein corona formation and internalization by phagocytic cells.

    Science.gov (United States)

    Ahmad Khanbeigi, Raha; Abelha, Thais Fedatto; Woods, Arcadia; Rastoin, Olivia; Harvey, Richard D; Jones, Marie-Christine; Forbes, Ben; Green, Mark A; Collins, Helen; Dailey, Lea Ann

    2015-03-09

    Conjugated polymer nanoparticles are being developed for a variety of diagnostic and theranostic applications. The conjugated polymer, F8BT, a polyfluorene derivative, was used as a model system to examine the biological behavior of conjugated polymer nanoparticle formulations stabilized with ionic (sodium dodecyl sulfate; F8BT-SDS; ∼207 nm; -31 mV) and nonionic (pegylated 12-hydroxystearate; F8BT-PEG; ∼175 nm; -5 mV) surfactants, and compared with polystyrene nanoparticles of a similar size (PS200; ∼217 nm; -40 mV). F8BT nanoparticles were as hydrophobic as PS200 (hydrophobic interaction chromatography index value: 0.96) and showed evidence of protein corona formation after incubation with serum-containing medium; however, unlike polystyrene, F8BT nanoparticles did not enrich specific proteins onto the nanoparticle surface. J774A.1 macrophage cells internalized approximately ∼20% and ∼60% of the F8BT-SDS and PS200 delivered dose (calculated by the ISDD model) in serum-supplemented and serum-free conditions, respectively, while cell association of F8BT-PEG was minimal (<5% of the delivered dose). F8BT-PEG, however, was more cytotoxic (IC50 4.5 μg cm(-2)) than F8BT-SDS or PS200. The study results highlight that F8BT surface chemistry influences the composition of the protein corona, while the properties of the conjugated polymer nanoparticle surfactant stabilizer used determine particle internalization and biocompatibility profile.

  19. Effects of π-conjugation attenuation on the photophysics and exciton dynamics of poly(p-phenylenevinylene) polymers incorporating 2,2'-bipyridines

    International Nuclear Information System (INIS)

    Chen, L. X.; Jager, W. J.; Niemczyk, M. P.; Wasielewski, M. R.

    1999-01-01

    The effect of π-conjugation attenuation on the photophysics and exciton dynamics of two conjugated polymers 1 and 2 are examined in solution. The structures of polymers 1 and 2 have 2,2'-bipyridyl-5-vinylene units that alternate with one and three 2,5-bis(n-decyloxy)-1,4-phenylenevinylene monomer units, respectively. The photophysics and exciton dynamics of polymers 1 and 2 were compared to those of the homopolymer, poly(2,5-bis(2'-ethylhexyloxy)-1,4-phenylenevinylene) (BEH-PPV). A series of changes in the photophysics of polymers 1 and 2 were found as a result of π-conjugation attenuation. These changes include blue shifts in absorption and emission spectra, spectral diffusion in stimulated emission, enhancement in photoluminescence quantum yields and lifetimes, and increases in photoinduced absorption intensities and lifetimes. These changes are systematically more pronounced in polymer 1 than in polymer 2 and are correlated with π-conjugation attenuation in the polymers due to twisting of the 2,2'-bipyridine groups about the 2,2' single bond. An exciton dynamics model involving an ensemble of initial exciton states localized on oligomeric segments within the polymer with different conjugation lengths is proposed to describe the observed differences between polymers 1 and 2 and BEH-PPV. When the electronic coupling between these segments is strong, the polymer displays characteristics that are close to those of a one-dimensional semiconductor. However, when these couplings are weakened by groups, such as the 2,2'-bipyridine that attenuate π-conjugation, the polymer displays properties of an ensemble of oligomers

  20. Efficient Supercapacitor Energy Storage Using Conjugated Microporous Polymer Networks Synthesized from Buchwald-Hartwig Coupling.

    Science.gov (United States)

    Liao, Yaozu; Wang, Haige; Zhu, Meifang; Thomas, Arne

    2018-03-01

    Supercapacitors have received increasing interest as energy storage devices due to their rapid charge-discharge rates, high power densities, and high durability. In this work, novel conjugated microporous polymer (CMP) networks are presented for supercapacitor energy storage, namely 3D polyaminoanthraquinone (PAQ) networks synthesized via Buchwald-Hartwig coupling between 2,6-diaminoanthraquinone and aryl bromides. PAQs exhibit surface areas up to 600 m 2 g -1 , good dispersibility in polar solvents, and can be processed to flexible electrodes. The PAQs exhibit a three-electrode specific capacitance of 576 F g -1 in 0.5 m H 2 SO 4 at a current of 1 A g -1 retaining 80-85% capacitances and nearly 100% Coulombic efficiencies (95-98%) upon 6000 cycles at a current density of 2 A g -1 . Asymmetric two-electrode supercapacitors assembled by PAQs show a capacitance of 168 F g -1 of total electrode materials, an energy density of 60 Wh kg -1 at a power density of 1300 W kg -1 , and a wide working potential window (0-1.6 V). The asymmetric supercapacitors show Coulombic efficiencies up to 97% and can retain 95.5% of initial capacitance undergo 2000 cycles. This work thus presents novel promising CMP networks for charge energy storage. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. Photovoltaic and Electroluminescence Characters in Hybrid ZnO and Conjugated Polymer Bulk Heterojunction Devices

    Institute of Scientific and Technical Information of China (English)

    LIU Jun-Peng; QU Sheng-Chun; XU Ying; CHEN Yong-Hai; ZENG Xiang-Bo; WANG Zhi-Jie; ZHOU Hui-Ying; WANG Zhan-Guo

    2007-01-01

    We report electroluminescence in hybrid ZnO and conjugated polymer poly[2-methoxy-5-(3',7'-dimethyloctyloxy)-1,4-phenylenevinylene] (MDMO-PPV) bulk heterojunction photovoltaic cells. Photoluminescence quenching experimental results indicate that the ultrafast photoinduced electron transfer occurs from MDMO-PPV to ZnO under illumination. The ultrafast photoinduced electron transfer effect is induced because ZnO has an electron affinity about 1.2 eV greater than that of MDMO-PPV. Electron 'back transfer' can occur if the interfacial barrier between ZnO and MDMO-PPV can be overcome by applying a substantial electric field. Therefore, electroluminescence action due to the fact that the back transfer effect can be observed in the ZnO: MDMO-PPV devices since a forward bias is applied. The photovoltaic and electroluminescence actions in the same ZnO: MDMO-PPV device can be induced by different injection ways: photoinjection and electrical injection. The devices are expected to provide an opportunity for dual functionality devices with photovoltaic effect and electroluminescence character.

  2. Impact of charge carrier injection on single-chain photophysics of conjugated polymers

    Energy Technology Data Exchange (ETDEWEB)

    Hofmann, Felix J.; Vogelsang, Jan, E-mail: jan.vogelsang@physik.uni-regensburg.de; Lupton, John M. [Institut für Experimentelle und Angewandte Physik, Universität Regensburg, Universitätsstrasse 31, 93053 Regensburg (Germany)

    2016-06-27

    Charges in conjugated polymer materials have a strong impact on the photophysics and their interaction with the primary excited state species has to be taken into account in understanding device properties. Here, we employ single-molecule spectroscopy to unravel the influence of charges on several photoluminescence (PL) observables. The charges are injected either stochastically by a photochemical process or deterministically in a hole-injection sandwich device configuration. We find that upon charge injection, besides a blue-shift of the PL emission and a shortening of the PL lifetime due to quenching and blocking of the lowest-energy chromophores, the non-classical photon arrival time distribution of the multichromophoric chain is modified towards a more classical distribution. Surprisingly, the fidelity of photon antibunching deteriorates upon charging, whereas one would actually expect the opposite: the number of chromophores to be reduced. A qualitative model is presented to explain the observed PL changes. The results are of interest to developing a microscopic understanding of the intrinsic charge-exciton quenching interaction in devices.

  3. Thickness dependent structural ordering, degradation and metastability in polysilane thin films: A photoluminescence study on representative σ-conjugated polymers

    International Nuclear Information System (INIS)

    Urbánek, Pavel; Kuřitka, Ivo

    2015-01-01

    We present a fundamental experimental study based on the fluorescence investigation of thin σ-conjugated polymer films, where the dependence of optoelectrical properties and UV degradation on film thickness ranging from nano- to microscale was studied. Such extensive and detailed study was performed for the first time and observed spectral shifts in emission and excitation spectra and UV degradation retardation point towards the conclusions that there exists a threshold thickness where the material degradation behavior, electron delocalization and structure suddenly change. The development of well aligned polymeric chain structure between the nano- and micrometer thickness (on the mesoscale) was shown responsible for the manifested phenomena. The material thicker than critical 500 nm has extremely small Stokes' shift, maximum extended σ-delocalization along the silicon polymer backbone and exhibits remarkable UV degradation slowdown and self-recovery ability. On the contrary, the electronic properties of thin films below 80 nm resemble those of random coils in solutions. The films of moderate thickness show relatively steep transition between these two modes of structural ordering and resulting properties. Altogether, we consider this complex phenomenon as a consequence of the mesoscale effect, which is an only recently introduced concept in polymer thin films. - Highlights: • Photoluminescence was used as a tool for structural investigation of polysilanes. • Primary study of strong dependence of thin polymer film structure on mesoscale. • A mesoscale effect observed for the first time on sigma conjugated polymers. • Conjugation length is dramatically extended in thicker films than in nanoscale. • Self-recovery effect was shown to be dependent on the mesoscale as well.

  4. Entanglements in Marginal Solutions: A Means of Tuning Pre-Aggregation of Conjugated Polymers with Positive Implications for Charge Transport

    KAUST Repository

    Hu, Hanlin

    2015-06-17

    The solution-processing of conjugated polymers, just like commodity polymers, is subject to solvent and molecular weight-dependent solubility, interactions and chain entanglements within the polymer, all of which can influence the crystallization and microstructure development in semi-crystalline polymers and consequently affect charge transport and optoelectronic properties. Disentanglement of polymer chains in marginal solvents was reported to work via ultrasonication, facilitating the formation of photophysically ordered polymer aggregates. In this contribution, we explore how a wide range of technologically relevant solvents and formulations commonly used in organic electronics influence chain entanglement and the aggregation behaviour of P3HT using a combination of rheological and spectrophotometric measurements. The specific viscosity of the solution offers an excellent indication of the degree of entanglements in the solution, which is found to be related to the solubility of P3HT in a given solvent. Moreover, deliberately disentangling the solution in the presence of solvophobic driving forces, leads consistently to formation of photophysically visible aggregates which is indicative of local and perhaps long range order in the solute. We show for a broad range of solvents and molecular weights that disentanglement ultimately leads to significant ordering of the polymer in the solid state and a commensurate increase in charge transport properties. In doing so we demonstrate a remarkable ability to tune the microstructure which has important implications for transport properties. We discuss its potential implications in the context of organic photovoltaics.

  5. Color optimization of conjugated-polymer/InGaN hybrid white light emitting diodes by incomplete energy transfer

    International Nuclear Information System (INIS)

    Chang, Chi-Jung; Lai, Chun-Feng; Madhusudhana Reddy, P.; Chen, Yung-Lin; Chiou, Wei-Yung; Chang, Shinn-Jen

    2015-01-01

    By using the wavelength conversion method, white light emitting diodes (WLEDs) were produced by applying mixtures of polysiloxane and fluorescent polymers on InGaN based light emitting diodes. UV curable organic–inorganic hybrid materials with high refractive index (1.561), compromised optical, thermal and mechanical properties was used as encapsulants. Red light emitting fluorescent FABD polymer (with 9,9-dioctylfluorene (F), anthracene (A) and 2,1,3-benzothiadiazole (B), and 4,7-bis(2-thienyl)-2,1,3-benzothiadiazole (D) repeating units) and green light emitting fluorescent FAB polymer were used as wavelength converters. The encapsulant/fluorescent polymer mixture and InGaN produce the white light by incomplete energy transfer mechanism. WLEDs with high color rendering index (CRI, about 93), and tunable correlated color temperature (CCT) properties can be produced by controlling the composition and chemical structures of encapsulating polymer and fluorescent polymer in hybrid materials, offering cool-white and neutral-white LEDs. - Highlights: • Highly efficient white light-emitting diodes (WLEDs) were produced. • Conjugated-polymer/InGaN hybrid WLEDs by incomplete energy transfer mechanism. • WLEDs with high color-rendering index and tunable correlated color temperature. • Polysiloxane encapsulant with superior optical, mechanical and thermal properties

  6. Entanglements in Marginal Solutions: A Means of Tuning Pre-Aggregation of Conjugated Polymers with Positive Implications for Charge Transport

    KAUST Repository

    Hu, Hanlin; Zhao, Kui; Fernandes, Nikhil J.; Boufflet, Pierre; Bannock, James Henry; Yu, Liyang; de Mello, John C; Stingelin, Natalie; Heeney, Martin; Giannelis, Emmanuel P.; Amassian, Aram

    2015-01-01

    The solution-processing of conjugated polymers, just like commodity polymers, is subject to solvent and molecular weight-dependent solubility, interactions and chain entanglements within the polymer, all of which can influence the crystallization and microstructure development in semi-crystalline polymers and consequently affect charge transport and optoelectronic properties. Disentanglement of polymer chains in marginal solvents was reported to work via ultrasonication, facilitating the formation of photophysically ordered polymer aggregates. In this contribution, we explore how a wide range of technologically relevant solvents and formulations commonly used in organic electronics influence chain entanglement and the aggregation behaviour of P3HT using a combination of rheological and spectrophotometric measurements. The specific viscosity of the solution offers an excellent indication of the degree of entanglements in the solution, which is found to be related to the solubility of P3HT in a given solvent. Moreover, deliberately disentangling the solution in the presence of solvophobic driving forces, leads consistently to formation of photophysically visible aggregates which is indicative of local and perhaps long range order in the solute. We show for a broad range of solvents and molecular weights that disentanglement ultimately leads to significant ordering of the polymer in the solid state and a commensurate increase in charge transport properties. In doing so we demonstrate a remarkable ability to tune the microstructure which has important implications for transport properties. We discuss its potential implications in the context of organic photovoltaics.

  7. Recent advances in polymer solar cells: realization of high device performance by incorporating water/alcohol-soluble conjugated polymers as electrode buffer layer.

    Science.gov (United States)

    He, Zhicai; Wu, Hongbin; Cao, Yong

    2014-02-01

    This Progress Report highlights recent advances in polymer solar cells with special attention focused on the recent rapid-growing progress in methods that use a thin layer of alcohol/water-soluble conjugated polymers as key component to obtain optimized device performance, but also discusses novel materials and device architectures made by major prestigious institutions in this field. We anticipate that due to drastic improvements in efficiency and easy utilization, this method opens up new opportunities for PSCs from various material systems to improve towards 10% efficiency, and many novel device structures will emerge as suitable architectures for developing the ideal roll-to-roll type processing of polymer-based solar cells. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. Transmissive-to-black fast electrochromic switching from a long conjugated pendant group and a highly dispersed polymer/SWNT

    KAUST Repository

    Zhang, Qiang

    2018-01-03

    In this study, a novel conjugated polymer, denoted as ECPblack, is synthesized. ECPblack demonstrated a unique electrochromic behavior with an ultrahigh contrast ratio (over 80%) in most of the visible regions, boasting an ultrahigh integrated contrast ratio of 71.8% between 380 nm and 880 nm. The long conjugated pendant group (pyrene) in ECPblack enhances the absorption in the blue region in its second oxidized state and results in transmissive-to-black electrochromic switching between the neutral state and the oxidized state. The transmissive-to-black electrochromic switching polymer with an ultrahigh contrast ratio could be especially attractive for applications in electronic displays. In addition, when polytriarylamine/nanotube (SWNT/P2) dispersion is doped in ECPblack, the response time of its electrochemical and electrochromic behaviors is further reduced. The electrochromic switching and bleaching time of SWNT/P2/ECPblack decreased by 73% and 80%, respectively. The improvement is caused by the phase separation of the rigid SWNT and the flexible polymer, which generates a rough surface morphology and provides more pathways for faster diffusion of counterions (ClO4-). The polymer/SWNT doping technique provides a simple way to accelerate ion diffusion in anodically coloring materials.

  9. Transmissive-to-black fast electrochromic switching from a long conjugated pendant group and a highly dispersed polymer/SWNT

    KAUST Repository

    Zhang, Qiang; Tsai, Chou-Yi; Abidin, Taufik; Jiang, Jyh-Chiang; Shie, Wan-Ru; Li, Lain-Jong; Liaw, Der-Jang

    2018-01-01

    In this study, a novel conjugated polymer, denoted as ECPblack, is synthesized. ECPblack demonstrated a unique electrochromic behavior with an ultrahigh contrast ratio (over 80%) in most of the visible regions, boasting an ultrahigh integrated contrast ratio of 71.8% between 380 nm and 880 nm. The long conjugated pendant group (pyrene) in ECPblack enhances the absorption in the blue region in its second oxidized state and results in transmissive-to-black electrochromic switching between the neutral state and the oxidized state. The transmissive-to-black electrochromic switching polymer with an ultrahigh contrast ratio could be especially attractive for applications in electronic displays. In addition, when polytriarylamine/nanotube (SWNT/P2) dispersion is doped in ECPblack, the response time of its electrochemical and electrochromic behaviors is further reduced. The electrochromic switching and bleaching time of SWNT/P2/ECPblack decreased by 73% and 80%, respectively. The improvement is caused by the phase separation of the rigid SWNT and the flexible polymer, which generates a rough surface morphology and provides more pathways for faster diffusion of counterions (ClO4-). The polymer/SWNT doping technique provides a simple way to accelerate ion diffusion in anodically coloring materials.

  10. A salt water battery with high stability and charging rates made from solution processed conjugated polymers with polar side chains

    KAUST Repository

    Moia, Davide

    2017-11-28

    We report a neutral salt water based battery which uses p-type and n-type solution processed polymer films as the cathode and the anode of the cell. The specific capacity of the electrodes (approximately 30 mAh cm-3) is achieved via formation of bipolarons in both the p-type and n-type polymers. By engineering ethylene glycol and zwitterion based side chains attached to the polymer backbone we facilitate rapid ion transport through the non-porous polymer films. This, combined with efficient transport of electronic charge via the conjugated polymer backbones, allowed the films to maintain constant capacity at high charge and discharge rates (>1000 C-rate). The electrodes also show good stability during electrochemical cycling (less than 30% decrease in capacity over >1000 cycles) and an output voltage up to 1.4 V. The performance of these semiconducting polymers with polar side-chains demonstrates the potential of this material class for fast-charging, water based electrochemical energy storage devices.

  11. Imparting chemical stability in nanoparticulate silver via a conjugated polymer casing approach.

    Science.gov (United States)

    Chang, Mincheol; Kim, Taejoon; Park, Hyun-Woo; Kang, Minjeong; Reichmanis, Elsa; Yoon, Hyeonseok

    2012-08-01

    Only limited information is available on the design and synthesis of functional materials for preventing corrosion of metal nanostructures. In the nanometer regime, even noble metals are subject to chemical attack. Here, the corrosion behavior of noble metal nanoparticles coated with a conjugated polymer nanolayer was explored for the first time. Specifically, electrochemical corrosion and sulfur tarnishing behaviors were examined for Ag-polypyrrole (PPy) core-shell nanoparticles using potentiodynamic polarization and spectrophotometric analysis, respectively. First, the Ag-PPy nanoparticles exhibited enhanced resistance to electrochemically induced corrosion compared to their exposed silver counterparts. Briefly, a neutral PPy shell provided the highest protection efficiency (75.5%), followed by sulfate ion- (61.3%) and dodecylbenzenesulfonate ion- (53.6%) doped PPy shells. However, the doping of the PPy shell with chloride ion induced an adverse effect (protection efficiency, -120%). Second, upon exposure to sulfide ions, the Ag-PPy nanoparticles preserved their morphology and colloidal stability while the bare silver analog underwent significant structural deformation. To further understand the function of the PPy shell as a protection layer for the silver core, the catalytic activity of the nanostructures was also evaluated. Using the reduction of 4-nitrophenol as a representative example of a catalytic reaction, the rate constant for that reduction using the PPy encased Ag nanoparticles was found to be 1.1 × 10(-3) s(-1), which is approximately 33% less than that determined for the parent silver. These results demonstrate that PPy can serve as both an electrical and chemical barrier for mitigating undesirable chemical degradation in corrosive environments, as well as provide a simple physical barrier to corrosive substances under appropriate conditions.

  12. Conformational assembly and biological properties of collagen mimetic peptides and their thermally responsive polymer conjugates

    Science.gov (United States)

    Krishna, Ohm Divyam

    2011-12-01

    Collagens are one of the most abundant proteins found in body tissues and organs, endowing structural integrity, mechanical strength, and multiple biological functions. Destabilized collagen inside human body leads to various degenerative diseases (ex. osteoarthritis) and ageing. This has continued to motivate the design of synthetic peptides and bio-synthetic polypeptides to closely mimic the native collagens in terms of triple helix structure and stability, potential for higher order assembly, and biological properties. However, the widespread application of de novo collagens has been limited in part by the need for hydroxylated proline in the formation of stable triple helical structures. To address this continued need, a hydroxyproline-free, thermally stable collagen-mimetic peptide (CLP-Cys) was rationally designed via the incorporation of electrostatically stabilized amino acid triplets. CLP-Cys was synthesized via solid phase peptide synthesis. The formation and stability of the triple helical structure were indicated via circular dichroism (CD) experiments and confirmed via differential scanning calorimetry (DSC) results. CLP-Cys also self-assembled into nano-rods and micro-fibrils, as evidenced via a combination of dynamic light scattering and transmission electron microscopy. Given the high thermal stability and its propensity for higher-order assembly, CLP-Cys was further functionalized at both the ends with a thermally responsive polymer, poly(diethylene glycol methyl ether methacrylate), (PDEGMEMA) to synthesize a biohybrid triblock copolymer. The CD results indicated that the triple helical form is retained, the thermal unfolding is sustained and helix to coil transition is reversible in the triblock hybrid context. The LCST of PDEGMEMA homopolymer (26 °C) is increased (to 35 °C) upon conjugation to the hydrophilic collagen peptide domain. Further, a combination of static light scattering, Cryo-SEM, TEM and confocal microscopy elucidated that the

  13. Nature of the Binding Interactions between Conjugated Polymer Chains and Fullerenes in Bulk Heterojunction Organic Solar Cells

    KAUST Repository

    Ravva, Mahesh Kumar

    2016-10-24

    Blends of π-conjugated polymers and fullerene derivatives are ubiquitous as the active layers of organic solar cells. However, a detailed understanding of the weak noncovalent interactions at the molecular level between the polymer chains and fullerenes is still lacking and could help in the design of more efficient photoactive layers. Here, using a combination of long-range corrected density functional theory calculations and molecular dynamic simulations, we report a thorough characterization of the nature of binding between fullerenes (C60 and PC61BM) and poly(benzo[1,2-b:4,5-b′]dithiophene–thieno[3,4-c]pyrrole-4,6-dione) (PBDTTPD) chains. We illustrate the variations in binding strength when the fullerenes dock on the electron-rich vs electron-poor units of the polymer as well as the importance of the role played by the polymer and fullerene side chains and the orientations of the PC61BM molecules with respect to the polymer backbones.

  14. Controlling morphology and chain aggregation in semiconducting conjugated polymers: the role of solvent on optical gain in MEH-PPV.

    Science.gov (United States)

    Lampert, Zach E; Reynolds, C Lewis; Papanikolas, John M; Aboelfotoh, M Osama

    2012-10-25

    We report the results of a detailed investigation that addresses the influence of polymer morphology and chain aggregation, as controlled by the chemical nature of the solvent, on the optical gain properties of the conjugated polymer poly[2-methoxy-5-(2'-ethylhexyloxy)-p-phenylene vinylene] (MEH-PPV). Using the variable stripe length technique in the picosecond regime, we have extensively studied the optical gain performance of asymmetric planar waveguides formed with thin MEH-PPV films spin-cast from concentrated chlorobenzene (CB) and tetrahydrofuran (THF) solutions onto thermally oxidized silicon substrates. CB and THF solvents were chosen based on their known ability to promote and effectively limit aggregate formation, respectively. Very large net gain coefficients are demonstrated, reaching values of 330 and 365 cm(-1), respectively, when optically pumping the waveguides with a maximum energy density of 85 μJ/cm(2). Our results clearly demonstrate that polymer morphology, and hence, the chain conformation dependence of the degree of aggregation in the films as controlled by the solvent, has minimal impact on the net gain. Moreover, the waveguides exhibit low loss coefficients of 10-20 cm(-1) at the ASE wavelength. These results question the importance of polymer morphology and aggregate formation in polymer-based optical devices operating at high excitation densities in the stimulated emission regime as would be characteristic of lasers and optical amplifiers.

  15. Conducting polymers, buckminsterfullerenes, and carbon nanotubes: optoelectronic materials based on architectural diversity of the π-conjugated structure

    International Nuclear Information System (INIS)

    Dai, L.

    2001-01-01

    Recent discovery of superconductivity in self assembled poly(3-hexylthiophene) two-dimensional conjugated sheets indicates the possible applications of plastics even in superconducting optoelectronic devices. Just as the discovery of C 60 has created an entirely new branch of carbon chemistry, the subsequent discovery of carbon nanotubes by lijima in 1991 opened up a new era in material science and nanotechnology. These elongated nanotubes consist of carbon hexagons arranged in a concentric manner with both ends normally capped by fullerene-like structures containing pentagons. Having a conjugated all-carbon structure with unusual molecular symmetries, fullerenes and carbon nanotubes also show interesting electronic, photonic, magnetic and mechanical properties, attractive for various applications, including optical limiters, photovoltaic cells and field emitting displays. For most of the above applications, it is highly desirable to prepare ordered/micropatterned conducting polymers, fullerenes, and carbon nanotubes. Although the microfabrication of conducting polymers has been an active research area for some years, it is a very recent development for fullerenes and carbon nanotubes. Recently, we doped polyaniline (PANI) with a hydrogensulfated fullerenol derivative containing multiple -OSO 3 H groups (i.e. C 60 (OH) 6 (OSO 3 H) 6 ) to produce three-dimensional PANI conductors with a room-temperature conductivity of up to 100 S cm -1 . This value of conductivity is about six orders of magnitude higher than the typical value for C 60 doped conducting polymers. Later, in collaboration with Wan's group at the Chinese Academy of Sciences, we have also synthesized PANI nanotubes via a self assembled C 60 (OH) 6 (OSO 3 H) 6 supramolecular template using (NH 4 ) 2 S 2 O 8 as an oxidant. These results, together with the more recent discovery of a hollow sphere, self assembled by the potassium salt of pentaphenyl fullerene (Ph 5 C 60 K) in water, clearly indicate that

  16. Graphene-induced band gap renormalization in polythiophene: a many-body perturbation study

    Science.gov (United States)

    Marsusi, F.; Fedorov, I. A.; Gerivani, S.

    2018-01-01

    Density functional theory and many-body perturbation theory at the G0W0 level are employed to study the electronic properties of polythiophene (PT) adsorbed on the graphene surface. Analysis of the charge density difference shows that substrate-adsorbate interaction leads to a strong physisorption and interfacial electric dipole moment formation. The electrostatic potential displays a  -0.19 eV shift in the graphene work function from its initial value of 4.53 eV, as the result of the interaction. The LDA band gap of the polymer does not show any change. However, the band structure exhibits weak orbital hybridizations resulting from slight overlapping between the polymer and graphene states wave functions. The interfacial polarization effects on the band gap and levels alignment are investigated at the G0W0 level and show a notable reduction of PT band gap compared to that of the isolated chain.

  17. Conductivity study of thermally stabilized RuO2/polythiophene nanocomposites

    Science.gov (United States)

    Hebbar, Vidyashree; Bhajantri, R. F.

    2018-04-01

    The polymer nanocomposites of Ruthenium oxide (RuO2) filled polythiophene (PT) were synthesized by polymerization using chemical method. The purity of the synthesized polymer composite is verified using X-Ray diffraction (XRD). The structural discrepancies of the RuO2 filled PT composites are studied by Fourier transform infrared (FT-IR) spectroscopy. The phase transition and thermal stability of the prepared composite is revised by thermal characterization such as differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). The DC conductivity of RuO2 filled PT composite in the form of pellets is calculated using current-voltage (I-V) characterization by two-probe method. The enhancement in conductivity with increased RuO2 content in PT matrix is examined, which is the required property for electrical and electronic applications in supercapacitors.

  18. A Possibility for Construction of an Iodine Cleaning System Based on Doping for π-Conjugated Polymers

    Directory of Open Access Journals (Sweden)

    Hiromasa Goto

    2011-05-01

    Full Text Available An iodine accumulation method using polyaniline (PANI and a textile composite is proposed. PANI/pulp paper sheets prepared by a paper making technique are suitable for iodine adsorption, because of good processability. The PANI-based paper sheets can be applied for iodine cleanup as air filters, water filters, and floorcloth. This concept may lead to a development of an iodine cleaning machine or iodine shield cloth based on π-conjugated polymer composites. In-situ vapor phase doping of iodine, observation of surface images, and IR measurements are carried out to examine iodine doping function for the PANI/pulp paper sheets.

  19. Low-temperature side-chain cleavage and decarboxylation of polythiophene esters by acid catalysis

    DEFF Research Database (Denmark)

    Søndergaard, Roar; Norrman, Kion; Krebs, Frederik C

    2012-01-01

    Solubility switching of polymers is very useful in thin layer processing of conjugated polymers, as it allows for multilayer processing and increases the stability of the polymer. Acid catalyzed thermocleavage of ester groups from thiophene polymers carrying primary, secondary, and tertiary subst...

  20. Thiophene Rings Improve the Device Performance of Conjugated Polymers in Polymer Solar Cells with Thick Active Layers

    NARCIS (Netherlands)

    Duan, C.; Gao, K.; Colberts, F. J. M.; Liu, F.; Meskers, S. C. J.; Wienk, M. M.; Janssen, R. A. J.

    2017-01-01

    Developing novel materials that tolerate thickness variations of the active layer is critical to further enhance the efficiency of polymer solar cells and enable large-scale manufacturing. Presently, only a few polymers afford high efficiencies at active layer thickness exceeding 200 nm and

  1. Pyridine-Based Conjugated Polymers: Photophysical Properties and Light- Emitting Diodes

    National Research Council Canada - National Science Library

    Epstein, A

    1997-01-01

    We study the photophysical properties of the pyridine-based polymers poly (p-pyridyl vinylene) (PPyV) and poly (p-pyridine) (PPy). The primary photoexcitations in the pyridine-based polymers are singlet excitons...

  2. Exciplex dynamics in a conjugated polymer blend of MDMO-PPV and PCNEPV

    NARCIS (Netherlands)

    Offermans, T.; Hal, van P.A.; Koetse, M.M.; Meskers, S.C.J.; Janssen, R.A.J.; Kafafi, Z.H.

    2005-01-01

    The photophysical properties of a solution processed blend of two semiconducting polymers with electron donating and electron accepting properties, respectively, as used in polymer photovoltaic devices have been investigated. In the binary mixture of

  3. Light-Emitting Devices Based on Pyridine-Containing Conjugated Polymers

    National Research Council Canada - National Science Library

    Wang, Y

    1997-01-01

    ...) as hole transporting/electron blocking polymer, which improves the device efficiency and brightness significantly due to the charge confinement and exciplex emission at the PVK/emitting polymer interface...

  4. Molecular designing of novel ternary copolymers of donor-acceptor polymers using genetic algorithm

    International Nuclear Information System (INIS)

    Arora, Vinita; Bakhshi, A.K.

    2010-01-01

    Graphical abstract: Alternate arrangement of donor acceptor moieties in the carbon backbone chain of an organic conjugated polymer is capable of inducing charge transfer and affects the electronic properties of the copolymer. Genetic algorithm along with simple NFC (negative factor counting) and IIM (inverse iteration method) has been used to optimize the properties of novel ternary copolymers based on polypyrrole PPy, polythiophene PTh and polyfuran PFu (as donor moieties) and containing >C=O and >C=CF 2 bridging units as acceptor moieties. - Abstract: An efficient designing route to novel ternary copolymers consisting of polypyrrole (PPy), polythiophene (PTh) and polyfuran (PFu) is developed with the help of genetic algorithm. Using the band structure results obtained from ab initio crystal orbital (CO) calculations, the electronic structures and conduction properties of real ternary copolymers based on donor acceptor type polymers are investigated. The electron rich heterocyclic rings in the backbone chain of the copolymer are joined together by electron withdrawing groups Y, carbonyl group (>C=O) and difluoromethylene group (>C=CF 2 ) in an attempt to design the conducting polymer with lowest band gap. A comparative study of various electronic properties is presented. The effects of substitution on the behaviour and properties of the copolymers as well as on the density of states (DOS) are discussed. Band gap decreases as a result of substitution on the polymer backbone chain due to decrease in ionization potential and increase in electron affinity values. This is expected to enhance the intrinsic conductivity of the resulting copolymer. Use of alternate donor acceptor moieties within the repeat units should maximize the extended π conjugation.

  5. Molecular designing of novel ternary copolymers of donor-acceptor polymers using genetic algorithm

    Energy Technology Data Exchange (ETDEWEB)

    Arora, Vinita [Department of Chemistry, University of Delhi, Delhi 110 007 (India); Bakhshi, A.K., E-mail: akbakhshi2000@yahoo.com [Department of Chemistry, University of Delhi, Delhi 110 007 (India)

    2010-08-03

    Graphical abstract: Alternate arrangement of donor acceptor moieties in the carbon backbone chain of an organic conjugated polymer is capable of inducing charge transfer and affects the electronic properties of the copolymer. Genetic algorithm along with simple NFC (negative factor counting) and IIM (inverse iteration method) has been used to optimize the properties of novel ternary copolymers based on polypyrrole PPy, polythiophene PTh and polyfuran PFu (as donor moieties) and containing >C=O and >C=CF{sub 2} bridging units as acceptor moieties. - Abstract: An efficient designing route to novel ternary copolymers consisting of polypyrrole (PPy), polythiophene (PTh) and polyfuran (PFu) is developed with the help of genetic algorithm. Using the band structure results obtained from ab initio crystal orbital (CO) calculations, the electronic structures and conduction properties of real ternary copolymers based on donor acceptor type polymers are investigated. The electron rich heterocyclic rings in the backbone chain of the copolymer are joined together by electron withdrawing groups Y, carbonyl group (>C=O) and difluoromethylene group (>C=CF{sub 2}) in an attempt to design the conducting polymer with lowest band gap. A comparative study of various electronic properties is presented. The effects of substitution on the behaviour and properties of the copolymers as well as on the density of states (DOS) are discussed. Band gap decreases as a result of substitution on the polymer backbone chain due to decrease in ionization potential and increase in electron affinity values. This is expected to enhance the intrinsic conductivity of the resulting copolymer. Use of alternate donor acceptor moieties within the repeat units should maximize the extended {pi} conjugation.

  6. Fabrication of molecular hybrid films of gold nanoparticle and polythiophene by covalent assembly

    Energy Technology Data Exchange (ETDEWEB)

    Sundaramurthy, Jayaraman, E-mail: jsu2@np.edu.sg [Department of Chemical & Biomolecular Engineering, National University of Singapore, Block E5, 4 Engineering Drive 4, 117576 (Singapore); Environmental & Water Technology Centre of Innovation, Ngee Ann Polytechnic, 599489 (Singapore); Dharmarajan, Rajarathnam [CERAR, University of South Australia, Mawson Lakes, SA 5095 (Australia); Srinivasan, M.P., E-mail: chesmp@nus.edu.sg [Department of Chemical & Biomolecular Engineering, National University of Singapore, Block E5, 4 Engineering Drive 4, 117576 (Singapore)

    2015-08-31

    This work demonstrates the fabrication of molecular hybrid films comprising gold nanoparticles (AuNPs) incorporated in covalently assembled, substituted polythiophene (poly(3-(2-bromoethoxy)ethoxymethylthiophene-2,5-diyl (PBrEEMT))) films by different surface chemistry routes. AuNPs are incorporated in the immobilized polythiophene matrix due to its affinity for amine and sulfur. The amount of AuNPs present depends on the nature of the incorporation, the extent of film coverage and interaction of thiophene and amine groups. PBrEEMT films functionalized with amine rich polyallylamine immobilize greater numbers of AuNPs due to more extensive gold–amine interactions. Covalent binding between AuNP and PBrEEMT films was accomplished by using pre-functionalised AuNPs (4-aminothiophenol functionalized AuNPs). Atomic force microscopy, field emission scanning electron microscopy and X-ray photoelectron spectroscopy were used to study the morphology and chemical constituents of assembled films. These approaches will pave the way for developing facile methods for nanoparticle incorporation and will also facilitate direct interaction of nanoparticles with the conducting polymer matrix and enhance the electrical properties of the films. - Highlights: • Covalent molecular assembly enabled the fabrication of molecular hybrid films. • Monomeric and polymeric species were employed as intermediate linkers. • Adopted approaches facilitated the direct interaction of gold nanoparticle in films. • The amount of nanoparticle incorporation depended on the extent of film coverage.

  7. Roll-to-Roll printed large-area all-polymer solar cells with 5% efficiency based on a low crystallinity conjugated polymer blend

    Science.gov (United States)

    Gu, Xiaodan; Zhou, Yan; Gu, Kevin; Kurosawa, Tadanori; Yan, Hongping; Wang, Cheng; Toney, Micheal; Bao, Zhenan

    The challenge of continuous printing in high efficiency large-area organic solar cells is a key limiting factor for their widespread adoption. We present a materials design concept for achieving large-area, solution coated all-polymer bulk heterojunction (BHJ) solar cells with stable phase separation morphology between the donor and acceptor. The key concept lies in inhibiting strong crystallization of donor and acceptor polymers, thus forming intermixed, low crystallinity and mostly amorphous blends. Based on experiments using donors and acceptors with different degree of crystallinity, our results showed that microphase separated donor and acceptor domain sizes are inversely proportional to the crystallinity of the conjugated polymers. This methodology of using low crystallinity donors and acceptors has the added benefit of forming a consistent and robust morphology that is insensitive to different processing conditions, allowing one to easily scale up the printing process from a small scale solution shearing coater to a large-scale continuous roll-to-roll (R2R) printer. We were able to continuously roll-to-roll slot die print large area all-polymer solar cells with power conversion efficiencies of 5%, with combined cell area up to 10 cm2. This is among the highest efficiencies realized with R2R coated active layer organic materials on flexible substrate. DOE BRIDGE sunshot program. Office of Naval Research.

  8. Preparation of new conductive polymer nanocomposites for cadmium removal from industrial wastewaters

    International Nuclear Information System (INIS)

    Zoleikani, Leila; Issazadeh, Hossein; ZareNezhad, Bahman

    2015-01-01

    Different conductive polymer nanocomposites have been synthesized, characterized and tested, regarding the removal of cadmium from industrial wastewaters. The chemical structure and morphology are studied by FTIR spectroscopy, scanning electron microscopy (SEM) and X-ray diffraction (XRD). The cadmium removal performance, using the produced polypyrrole, polyaniline and polythiophene nanocomposites, are about 40.2 %, 59 % and 99.94 %, respectively, suggesting the superior performance of synthesized polythiophene conductive nanocomposite for cadmium removal from industrial wastewaters. It is shown that the Langmuir adsorption model can be used for accurate description of cadmium removal mechanism using different synthesized conductive nanocomposites. Keywords : wastewater, nanocomposite, polythiophene, cadmium removal, conductive polymer.

  9. Naphtho[1,2-b:5,6-b']dithiophene-Based Conjugated Polymers for Fullerene-Free Inverted Polymer Solar Cells.

    Science.gov (United States)

    Jiang, Zhaoyan; Li, Huan; Wang, Zhen; Zhang, Jianqi; Zhang, Yajie; Lu, Kun; Wei, Zhixiang

    2018-03-23

    Three novel copolymers based on zigzag naphthodithiophene (zNDT) with different aromatic rings as π bridges and different core side substitutions are designed and synthesized (PzNDT-T-1,3-bis(4-(2-ethylhexyl)-thiophen-2-yl)-5,7-bis(2-ethylhexyl)benzo[1,2-c:4,5-c']-dithiophene-4,8-dione (BDD), PzNDT-TT-BDD, and PzNDTP-T-BDD, respectively). The 2D conjugation structure and molecular planarity of the polymers can be effectively altered through the modification of conjugated side chains and π-bridges. These alterations contribute to the variation in energy levels, light absorption capacity, and morphology compatibility of the polymers. When blended with the nonfullerene acceptor (2,2'-[(4,4,9,9-tetrahexyl-4,9-dihydro-sindaceno[1,2-b:5,6-b']dithiophene-2,7-diyl)bis[methylidyne(3-oxo-1H-indene-2,1(3H)-diylidene)

  10. Bispecific antibody complex pre-targeting and targeted delivery of polymer drug conjugates for imaging and therapy in dual human mammary cancer xenografts. Targeted polymer drug conjugates for cancer diagnosis and therapy

    Energy Technology Data Exchange (ETDEWEB)

    Khaw, Ban-An; Gada, Keyur S.; Patil, Vishwesh; Panwar, Rajiv; Mandapati, Savitri [Northeastern University, Department of Pharmaceutical Sciences, Bouve College of Health Sciences, School of Pharmacy, Boston, MA (United States); Hatefi, Arash [Rutgers University, Department of Pharmaceutics, New Brunswick, NJ (United States); Majewski, Stan [West Virginia University, Department of Radiology, Morgantown, WV (United States); Weisenberger, Andrew [Thomas Jefferson National Accelerator Facility, Jefferson Lab, Newport News, VA (United States)

    2014-08-15

    Doxorubicin, a frontline chemotherapeutic agent, limited by its cardiotoxicity and other tissue toxicities, was conjugated to N-terminal DTPA-modified polyglutamic acid (D-Dox-PGA) to produce polymer pro-drug conjugates. D-Dox-PGA or Tc-99 m labeled DTPA-succinyl-polylysine polymers (DSPL) were targeted to HER2-positive human mammary carcinoma (BT-474) in a double xenografted SCID mouse model also hosting HER2-negative human mammary carcinoma (BT-20). After pretargeting with bispecific anti-HER2-affibody-anti-DTPA-Fab complexes (BAAC), anti-DTPA-Fab or only phosphate buffered saline, D-Dox-PGA or Tc-99 m DSPL were administered. Positive therapeutic control mice were injected with Dox alone at maximum tolerated dose (MTD). Only BT-474 lesions were visualized by gamma imaging with Tc-99 m-DSPL; BT-20 lesions were not. Therapeutic efficacy was equivalent in mice pretargeted with BAAC/targeted with D-Dox-PGA to mice treated only with doxorubicin. There was no total body weight (TBW) loss at three times the doxorubicin equivalent MTD with D-Dox-PGA, whereas mice treated with doxorubicin lost 10 % of TBW at 2 weeks and 16 % after the second MTD injection leading to death of all mice. Our cancer imaging and pretargeted therapeutic approaches are highly target specific, delivering very high specific activity reagents that may result in the development of a novel theranostic application. HER/2 neu specific affibody-anti-DTPA-Fab bispecific antibody pretargeting of HER2 positive human mammary xenografts enabled exquisite targeting of polymers loaded with radioisotopes for molecular imaging and doxorubicin for effective therapy without the associating non-tumor normal tissue toxicities. (orig.)

  11. High-Performance All-Polymer Solar Cells Achieved by Fused Perylenediimide-Based Conjugated Polymer Acceptors.

    Science.gov (United States)

    Yin, Yuli; Yang, Jing; Guo, Fengyun; Zhou, Erjun; Zhao, Liancheng; Zhang, Yong

    2018-05-09

    We report three n-type polymeric electron acceptors (PFPDI-TT, PFPDI-T, and PFPDI-Se) based on the fused perylene diimide (FPDI) and thieno[3,2- b]thiophene, thiophene, or selenophene units for all-polymer solar cells (all-PSCs). These FPDI-based polymer acceptors exhibit strong absorption between 350 and 650 nm with wide optical bandgap of 1.86-1.91 eV, showing good absorption compensation with the narrow bandgap polymer donor. The lowest unoccupied molecular orbital (LUMO) energy levels were located at around -4.11 eV, which are comparable with those of the fullerene derivatives and other small molecular electron acceptors. The conventional all-PSCs based on the three polymer acceptors and PTB7-Th as polymer donor gave remarkable power conversion efficiencies (PCEs) of >6%, and the PFPDI-Se-based all-PSC achieved the highest PCE of 6.58% with a short-circuit current density ( J sc ) of 13.96 mA/cm 2 , an open-circuit voltage ( V oc ) of 0.76 V, and a fill factor (FF) of 62.0%. More interestingly, our results indicate that the photovoltaic performances of the FPDI-based polymer acceptors are mainly determined by the FPDI unit with a small effect from the comonomers, which is quite different from the others reported rylenediimide-based polymer acceptors. This intriguing phenomenon is speculated as the huge geometry configuration of the FPDI unit, which minimizes the effect of the comonomer. These results highlight a promising future for the application of the FPDI-based polymer acceptors in the highly efficient all-PSCs.

  12. Fluorinated arene, imide and unsaturated pyrrolidinone based donor acceptor conjugated polymers: Synthesis, structure-property and device studies

    Science.gov (United States)

    Liyanage, Arawwawala Don Thilanga

    After the discovery of doped polyacetylene, organic semiconductor materials are widely studied as high impending active components in consumer electronics. They have received substantial consideration due to their potential for structural tailoring, low cost, large area and mechanically flexible alternatives to common inorganic semiconductors. To acquire maximum use of these materials, it is essential to get a strong idea about their chemical and physical nature. Material chemist has an enormous role to play in this novel area, including development of efficient synthetic methodologies and control the molecular self-assembly and (opto)-electronic properties. The body of this thesis mainly focuses on the substituent effects: how different substituents affect the (opto)-electronic properties of the donor-acceptor (D-A) conjugated polymers. The main priority goes to understand, how different alkyl substituent effect to the polymer solubility, crystallinity, thermal properties (e.g.: glass transition temperature) and morphological order. Three classes of D-A systems were extensively studied in this work. The second chapter mainly focuses on the synthesis and structure-property study of fluorinated arene (TFB) base polymers. Here we used commercially available 1,4-dibromo-2,3,5,6-tetrafluorobenzene (TFB) as the acceptor material and prepare several polymers using 3,3'-dialkyl(3,3'-R2T2) or 3,3'-dialkoxy bithiophene (3,3'-RO2T2) units as electron donors. A detail study was done using 3,3'-bithiophene donor units incorporating branched alkoxy-functionalities by systematic variation of branching position and chain length. The study allowed disentangling the branching effects on (i) aggregation tendency, intermolecular arrangement, (iii) solid state optical energy gaps, and (iv) electronic properties in an overall consistent picture, which might guide future polymer synthesis towards optimized materials for opto-electronic applications. The third chapter mainly focused on

  13. Influence of acceptor on charge mobility in stacked π-conjugated polymers

    Science.gov (United States)

    Sun, Shih-Jye; Menšík, Miroslav; Toman, Petr; Gagliardi, Alessio; Král, Karel

    2018-02-01

    We present a quantum molecular model to calculate mobility of π-stacked P3HT polymer layers with electron acceptor dopants coupled next to side groups in random position with respect to the linear chain. The hole density, the acceptor LUMO energy and the hybridization transfer integral between the acceptor and polymer were found to be very critical factors to the final hole mobility. For a dopant LUMO energy close and high above the top of the polymer valence band we have found a significant mobility increase with the hole concentration and with the dopant LUMO energy approaching the top of the polymer valence band. Higher mobility was achieved for small values of hybridization transfer integral between polymer and the acceptor, corresponding to the case of weakly bound acceptor. Strong couplings between the polymer and the acceptor with Coulomb repulsion interactions induced from the electron localizations was found to suppress the hole mobility.

  14. Conjugated Polymers Containing BODIPY and Fluorene Units for Sensitive Detection of CN− Ions: Site-Selective Synthesis, Photo-Physical and Electrochemical Properties

    Directory of Open Access Journals (Sweden)

    Tian He

    2017-10-01

    Full Text Available Conjugated polymers containing distinct molecular units are expected to be very interesting because of their unique properties endowed by these units and the formed conjugated polymers. Herein, four new conjugated copolymers based on fluorene and 4,4’-difluoro-4-bora-3a,4a-diaza-s-indacene (BODIPY have been designed and synthesized via Sonogashira polymerization. The fluorene unit was attached to the 3,5- or 2,6-positions of BODIPY by ethynylenes or p-diacetylenebenzene. The obtained polymers show good thermal stability and broad absorption in the wavelength range from 300 to 750 nm. The effects of site-selective copolymerization and conjugation length along the polymer backbone on the optoelectronic and electrochemical properties of these copolymers were systematically studied by UV-Vis spectroscopy, photoluminescence (PL and cyclic voltammetry. Besides, it is found that the BODIPY-based copolymers exhibit selectively sensitive responses to cyanide anions, resulting in obvious change of UV-Vis absorption spectra and significant fluorescence quenching of the polymers among various common anions.

  15. Application of Thin Films of Conjugated Polymers in Novel LED's and Liquid Crystal 'Light Valves'

    National Research Council Canada - National Science Library

    MacDiarmid, A

    1997-01-01

    .... Flexible, completely organic polymer dispersed liquid crystal light valves have been fabricated from transparent plastic substrates on which a conducting film of polypyrrole has been deposited...

  16. Fused thiophene-based conjugated polymers and their use in optoelectronic devices

    Science.gov (United States)

    Facchetti, Antonio; Marks, Tobin J.; Takai, Atsuro; Seger, Mark; Chen; , Zhihua

    2017-07-18

    The present teachings relate to polymeric compounds and their use as organic semiconductors in organic and hybrid optical, optoelectronic, and/or electronic devices such as photovoltaic cells, light emitting diodes, light emitting transistors, and field effect transistors. The disclosed compounds generally include as repeating units at least one annulated thienyl-vinylene-thienyl (TVT) unit and at least one other pi-conjugated unit. The annulated TVT unit can be represented by the formula: ##STR00001## where Cy.sup.1 and Cy.sup.2 can be a five- or six-membered carbocyclic ring. The annulated TVT unit can be optionally substituted at any available ring atom(s), and can be covalently linked to the other pi-conjugated unit via either the thiophene rings or the carbocyclic rings Cy.sup.1 and Cy.sup.2. The other pi-conjugated unit can be a conjugated linear linker including one or more unsaturated bonds, or a conjugated cyclic linker including one or more carbocyclic and/or heterocyclic rings.

  17. Alkylated indacenodithieno[3,2-b]thiophene-based all donor ladder-type conjugated polymers for organic thin film transistors

    KAUST Repository

    Lu, Rimei

    2018-01-29

    We report the synthesis of a series of indacenodithieno[3,2-b]thiophene (IDTT) based conjugated polymers by copolymerization with three different electron rich co-monomers [thiophene (T), thieno[3,2-b]thiophene (TT) and dithieno[3,2-b:2\\',3\\'-d]thiophene (DTT)] under Stille coupling conditions. The resulting all-donor polymers show very good solubility in common solvents and exhibit similar optical, thermal and electronic properties. However, the performance of these semiconductors in thin film transistor devices varied and was highly dependent on the nature of the co-monomer. All polymers exhibited unipolar p-type charge transport behaviour, with the mobility values following the trend of IDTT-TT>IDTT-DTT>IDTT-T. The peak saturation mobility value of IDTT-TT was extracted to be 1.1 cm2V-1s-1, amongst the highest mobility for all-donor conjugated polymers reported to date.

  18. Thermocleavable π‐Conjugated Polymers – Synthesis and photovoltaic applications

    DEFF Research Database (Denmark)

    Petersen, Martin Helgesen

    Polymer solar cells (plastic solar cells) have seen remarkable improvements in recent years where power conversion efficiencies of up to 6% have been reported for small area devices. However in terms of stability polymer solar cells degrade during illumination and in the dark leading to operational...... lifetimes that are generally very poor. There has been a recent interest in the operational stability of devices and more importantly on the understanding of why devices and materials break down. This has lead to the discovery of a new class of materials that enable exceptionally long device lifetimes...... (>20000 hours). This Ph.D. thesis describes the synthesis, characterization and photovoltaic applications of these novel polymer materials. A key feature of these materials is that solubilizing thermocleavable alkyl ester side chains are introduced on the polymer backbone. The side chains make the polymer...

  19. Hybrid fluorescent nanoparticles fabricated from pyridine-functionalized polyfluorene-based conjugated polymer as reversible pH probes over a broad range of acidity-alkalinity

    International Nuclear Information System (INIS)

    Cui, Haijun; Chen, Ying; Li, Lianshan; Tang, Zhiyong; Wu, Yishi; Fu, Hongbing; Tian, Zhiyuan

    2014-01-01

    Conjugated polymer nanoparticles (CPNs) were developed based on a polyfluorene-based conjugated polymer with thiophene units carrying pyridyl moieties incorporated in the backbone of polymer chains (PFPyT). Hybrid CPNs fabricated from PFPyT and an amphiphilic polymer (NP1) displayed pH-sensitive fluorescence emission features in the range from pH 4.8 to 13, which makes them an attractive nanomaterial for wide range optical sensing of pH values. The fluorescence of hybrid CPNs based on chemically close polyfluorene derivatives without pyridyl moieties (NP3), in contrast, remains virtually unperturbed by pH values in the same range. The fluorescence emission features of NP1 underwent fully reversible changes upon alternating acidification/basification of aqueous dispersions of the CPNs and also displayed excellent repeatability. The observed pH sensing properties of NP1 are attributed to protonation/deprotonation of the nitrogen atoms of the pyridine moieties. This, in turn, leads to the redistribution of electron density of pyridine moieties and their participation in the π-conjugation within the polymer main chains. The optically transparent amphiphilic polymers also exerted significant influence on the pH sensing features of the CPNs, likely by acting as proton sponge and/or acid chaperone. (author)

  20. Non-covalent functionalization of carbon nanotubes: Controlling Chirality Selectivity via Alkyl Groups of Conjugated Co-Polymers

    Science.gov (United States)

    Weight, Braden; Gifford, Brendan; Kilina, Svetlana

    Carbon nanotubes (CNTs) play an important role in nanotechnology, including electronics, chemical sensors, and solar cells. Their electronic and optical properties depend on the size and geometry (chirality) of the nanotube. However, one main concern regarding nanotube application in optoelectronic devices is the difficulty of separating them based upon chirality after synthesis, as all known synthesis methods produce more than one chirality simultaneously. To get around this, one method is the functionalization of the CNTs via non-covalent bonding of co-polymers by wrapping them around the tube. We use force field simulations to explore the effects of various structural manipulations to the co-polymer 9,9-dialkylfluorenyl-2,7-diyl bipyridine (PFO-BPY) to find the preferential mechanisms of selective interactions between the PFO-BPY and CNTs of various chiralities. In particular, we focus on the effect of the branching in alkyl side-groups of PFO-BPY on their binding to the CNT surface. We have observed correlations between the side-group structures and their wrapping morphology on the CNT-Polymer interactions. Our calculations demonstrate that the branching in the position closest to the conjugated backboned results in the strongest interaction with all CNT. This research was supported by the National Science Foundation (CHE 1413614) and the Center for Computationally-Assisted Science and Technology at NDSU.

  1. Molecular properties of conjugates formed by synthetic hydrophilic polymers and sterically hindered phenols

    Czech Academy of Sciences Publication Activity Database

    Domnina, N. S.; Sergeeva, O. Yu.; Koroleva, A. N.; Rakitina, O. V.; Dobrun, L. A.; Filippov, Sergey K.; Mikhailova, M. E.; Lezov, A. V.

    2010-01-01

    Roč. 52, č. 9 (2010), s. 900-906 ISSN 0965-545X Institutional research plan: CEZ:AV0Z40500505 Keywords : antioxidant * conjugates * light scattering Subject RIV: CD - Macromolecular Chemistry Impact factor: 0.659, year: 2010

  2. Ionic π-Conjugated Polymer Networks by Catalyst-Free Polymerization, Photoluminescence and Gas Sorption Behavior

    Czech Academy of Sciences Publication Activity Database

    Faukner, T.; Zukal, Arnošt; Brus, Jiří; Zedník, J.; Sedláček, J.

    2016-01-01

    Roč. 217, č. 17 (2016), s. 1886-1898 ISSN 1022-1352 R&D Projects: GA ČR(CZ) GA15-09637S Institutional support: RVO:61388955 ; RVO:61389013 Keywords : conjugated polyacetylene * ethanol vapors * gas sorption Subject RIV: CF - Physical ; Theoretical Chemistry; CD - Macromolecular Chemistry (UMCH-V) Impact factor: 2.500, year: 2016

  3. Evolution of in situ conductivity of polythiophene deposits by potential cycling

    Energy Technology Data Exchange (ETDEWEB)

    Zotti, G.; Schiavon, G. (Ist. di Polarografia ed Elettrochimica Preparativa, Consiglio Nazionale delle Ricerche, Padua (Italy))

    1990-12-01

    In situ conductivity of polythiophene (PT) deposits from anodic coupling of thiophene (T), bithiophene (BT) and terthiophene (TT) increases with redox switching to an extent which depends on the monomer. Changes are considerable with TT, minor with BT and negligible with T, involving extra oxidative charges with the same trend, and are paralleled by evolution of electronic and infrared spectra and cyclic voltammograms. Results are explained by the occurrence of solid-state polymerization of oligomers leading ultimately to the same polymer with a conductivity of 1-3 S cm{sup -1}. PT from thiophene is much less conducting (0.06 S cm{sup -1}), because of oxidative degradation during deposition. (orig.).

  4. Alkylated indacenodithieno[3,2-b]thiophene-based all donor ladder-type conjugated polymers for organic thin film transistors

    KAUST Repository

    Lu, Rimei; Han, Yang; Zhang, Weimin; Zhu, Xiuxiu; Fei, Zhuping; Hodsden, Thomas; Anthopoulos, Thomas D.; Heeney, Martin

    2018-01-01

    We report the synthesis of a series of indacenodithieno[3,2-b]thiophene (IDTT) based conjugated polymers by copolymerization with three different electron rich co-monomers [thiophene (T), thieno[3,2-b]thiophene (TT) and dithieno[3,2-b:2',3'-d

  5. Synthesis and functions of well-defined polymer-drug conjugates as efficient nanocarriers for intravesical chemotherapy of bladder cancer(a).

    Science.gov (United States)

    Yu, Qingsong; Zhang, Jiajing; Zhang, Guan; Gan, Zhihua

    2015-04-01

    Novel poly(ethylene glycol) and poly(N-(2-hydroxypropyl)methacrylamide) block copolymer (PEG-b-PHPMA) with well-defined composition was synthesized by RAFT polymerization. Folate and doxorubicin (DOX) were quantitatively introduced into the copolymer. The influences of folate content and pH value on folate receptor (FR) mediated cell endocytosis and pH-responsive DOX release were studied. It has been demonstrated that minimum folate content is needed for the enrichment of hydrophobic folate on the hydrophilic part of polymer conjugates. The cytotoxicity of targetable polymer drug conjugates was much higher than that of non-targetable ones and free DOX. It could be concluded that the folate plays a significant role in targeting and internalization of the conjugates against bladder cancer cells. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. Azaisoindigo conjugated polymers for high performance n-type and ambipolar thin film transistor applications

    KAUST Repository

    Yue, Wan

    2016-09-28

    Two new alternating copolymers, PAIIDBT and PAIIDSe have been prepared by incorporating a highly electron deficient azaisoindigo core. The molecular structure and packing of the monomer is determined from the single crystal X-ray diffraction. Both polymers exhibit high EAs and highly planar polymer backbones. When polymers are used as the semiconducting channel for solution-processed thin film transistor application, good properties are observed. A–A type PAIIDBT exhibits unipolar electron mobility as high as 1.0 cm2 V−1 s−1, D–A type PAIIDSe exhibits ambipolar charge transport behavior with predominately electron mobility up to 0.5 cm2 V−1 s−1 and hole mobility to 0.2 cm2 V−1 s−1. The robustness of the extracted mobility values are also commented on in detail. Molecular orientation, thin film morphology and energetic disorder of both polymers are systematically investigated.

  7. .Pi.-conjugated donor and donor-acceptor metallo-polymers

    Czech Academy of Sciences Publication Activity Database

    Wild, A.; Schlütter, F.; Pavlov, G. M.; Friebe, Ch.; Festag, G.; Winter, A.; Hager, M. D.; Cimrová, Věra; Schubert, U.S.

    2010-01-01

    Roč. 31, 9-10 (2010), s. 868-874 ISSN 1022-1336 R&D Projects: GA MŠk(CZ) 1M06031; GA AV ČR IAA4050409 Institutional research plan: CEZ:AV0Z40500505 Keywords : analytical ultracentrifugation * conducting polymers * metallo-polymers Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 4.371, year: 2010

  8. Conjugated Polymer Chains Confined in Vertical Nanocylinders of a Block-Copolymer Film: Preparation, Characterization, and Optoelectronic Function

    KAUST Repository

    Dong, Ban Xuan; Honmou, Yoshihiro; Komiyama, Hideaki; Furumaki, Shu; Iyoda, Tomokazu; Vacha, Martin

    2013-01-01

    Hybrid materials composed of phase-separated block copolymer films and conjugated polymers of the phenylenevinylene family (PPV) are prepared. The PPV chains are embedded in vertical cylinders of nanometer diameter in the block-copolymer films. The cylinders span continuously the whole film thickness of 70 nm. Incorporation of the PPV chains into the one-dimensional cylinders leads to modified photoluminescence spectra and to large absorption anisotropy. The hybrid films show electroluminescence from the PPV chains in a simple light-emitting device at minute doping concentrations, and also exhibit a factor of 19 increase in electron transport efficiency along the single PPV chains. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. Detection of bisphenol A in food packaging based on fluorescent conjugated polymer PPESO3 and enzyme system.

    Science.gov (United States)

    Huang, Hui; Li, Yongxin; Liu, Jintong; Tong, Jin; Su, Xingguang

    2015-10-15

    Bisphenol A (BPA) is a kind of carcinogen, which can interfere with the body's endocrine system. In this paper, a new kind of fluorescent sensor for BPA detection was established based on the fluorescent conjugated polymer PPESO3. The oxidative product of BPA is able to quench PPESO3 in the presence of HRP and H2O2, and the quenched PL intensity of PPESO3 was proportionally to the concentration of BPA in the range of 1-100 μmol/L with a detection limit of 4 × 10(-7) mol/L. The proposed method has been applied to detect BPA in eight food packaging samples with satisfactory results. The proposed method has the potential for the assay of BPA in food or food packaging samples. Copyright © 2015 Elsevier Ltd. All rights reserved.

  10. Photonics of a conjugated organometallic Pt-Ir polymer and its model compounds exhibiting hybrid CT excited states.

    Science.gov (United States)

    Soliman, Ahmed M; Fortin, Daniel; Zysman-Colman, Eli; Harvey, Pierre D

    2012-04-13

    Trans- dichlorobis(tri-n-butylphosphine)platinum(II) reacts with bis(2- phenylpyridinato)-(5,5'-diethynyl-2,2'-bipyridine)iridium(III) hexafluorophosphate to form the luminescent conjugated polymer poly[trans-[(5,5'-ethynyl-2,2'-bipyridine)bis(2- phenylpyridinato)-iridium(III)]bis(tri-n-butylphosphine)platinum(II)] hexafluorophosphate ([Pt]-[Ir])n. Gel permeation chromatography indicates a degree of polymerization of 9 inferring the presence of an oligomer. Comparison of the absorption and emission band positions and their temperature dependence, emission quantum yields, and lifetimes with those for models containing only the [Pt] or the [Ir] units indicates hybrid excited states including features from both chromophores. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  11. Conjugated Polymer Chains Confined in Vertical Nanocylinders of a Block-Copolymer Film: Preparation, Characterization, and Optoelectronic Function

    KAUST Repository

    Dong, Ban Xuan

    2013-01-15

    Hybrid materials composed of phase-separated block copolymer films and conjugated polymers of the phenylenevinylene family (PPV) are prepared. The PPV chains are embedded in vertical cylinders of nanometer diameter in the block-copolymer films. The cylinders span continuously the whole film thickness of 70 nm. Incorporation of the PPV chains into the one-dimensional cylinders leads to modified photoluminescence spectra and to large absorption anisotropy. The hybrid films show electroluminescence from the PPV chains in a simple light-emitting device at minute doping concentrations, and also exhibit a factor of 19 increase in electron transport efficiency along the single PPV chains. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. Flexible organic/inorganic hybrid solar cells based on conjugated polymer and ZnO nanorod array

    International Nuclear Information System (INIS)

    Tong, Fei; Kim, Kyusang; Martinez, Daniel; Thapa, Resham; Ahyi, Ayayi; Williams, John; Park, Minseo; Kim, Dong-Joo; Lee, Sungkoo; Lim, Eunhee; Lee, Kyeong K

    2012-01-01

    We report on the photovoltaic characteristics of organic/inorganic hybrid solar cells fabricated on ‘flexible’ transparent substrates. The solar cell device is composed of ZnO nanorod array and the bulk heterojunction structured organic layer which is the blend of poly(3-hexylthiophene) (P3HT) and (6,6)-phenyl C61 butyric acid methyl ester (PCBM). The ZnO nanorod array was grown on indium tin oxide (ITO)-coated polyethylene terephthalate (PET) substrates via a low-temperature (85 °C) aqueous solution process. The blend solution consisting of conjugated polymer P3HT and fullerene PCBM was spin coated at a low spinning rate of 400 rpm on top of the ZnO nanorod array structure and then the photoactive layer was slow dried at room temperature in air to promote its infiltration into the nanorod network. As a top electrode, silver was sputtered on top of the photoactive layer. The flexible solar cell with the structure of PET/ITO/ZnO thin film/ZnO nanorods/P3HT:PCBM/Ag exhibited a photovoltaic performance with an open circuit voltage (V OC ) of 0.52 V, a short circuit current density (J SC ) of 9.82 mA cm −2 , a fill factor (FF) of 35% and a power conversion efficiency (η) of 1.78%. All the measurements were performed under 100 mW cm −2 of illumination with an air mass 1.5 G filter. To the best of our knowledge, this is the first presentation of investigation into the fabrication and characterization of organic/inorganic hybrid solar cells based on bulk heterojunction structured conjugated polymer/fullerene photoactive layer and ZnO nanorod array constructed on flexible transparent substrates. (paper)

  13. Fluorescence polarization measures energy funneling in single light-harvesting antennas--LH2 vs conjugated polymers.

    Science.gov (United States)

    Camacho, Rafael; Tubasum, Sumera; Southall, June; Cogdell, Richard J; Sforazzini, Giuseppe; Anderson, Harry L; Pullerits, Tõnu; Scheblykin, Ivan G

    2015-10-19

    Numerous approaches have been proposed to mimic natural photosynthesis using artificial antenna systems, such as conjugated polymers (CPs), dendrimers, and J-aggregates. As a result, there is a need to characterize and compare the excitation energy transfer (EET) properties of various natural and artificial antennas. Here we experimentally show that EET in single antennas can be characterized by 2D polarization imaging using the single funnel approximation. This methodology addresses the ability of an individual antenna to transfer its absorbed energy towards a single pool of emissive states, using a single parameter called energy funneling efficiency (ε). We studied individual peripheral antennas of purple bacteria (LH2) and single CP chains of 20 nm length. As expected from a perfect antenna, LH2s showed funneling efficiencies close to unity. In contrast, CPs showed lower average funneling efficiencies, greatly varying from molecule to molecule. Cyclodextrin insulation of the conjugated backbone improves EET, increasing the fraction of CPs possessing ε = 1. Comparison between LH2s and CPs shows the importance of the protection systems and the protein scaffold of LH2, which keep the chromophores in functional form and at such geometrical arrangement that ensures excellent EET.

  14. Fluorescence polarization measures energy funneling in single light-harvesting antennas—LH2 vs conjugated polymers

    Science.gov (United States)

    Camacho, Rafael; Tubasum, Sumera; Southall, June; Cogdell, Richard J.; Sforazzini, Giuseppe; Anderson, Harry L.; Pullerits, Tõnu; Scheblykin, Ivan G.

    2015-10-01

    Numerous approaches have been proposed to mimic natural photosynthesis using artificial antenna systems, such as conjugated polymers (CPs), dendrimers, and J-aggregates. As a result, there is a need to characterize and compare the excitation energy transfer (EET) properties of various natural and artificial antennas. Here we experimentally show that EET in single antennas can be characterized by 2D polarization imaging using the single funnel approximation. This methodology addresses the ability of an individual antenna to transfer its absorbed energy towards a single pool of emissive states, using a single parameter called energy funneling efficiency (ɛ). We studied individual peripheral antennas of purple bacteria (LH2) and single CP chains of 20 nm length. As expected from a perfect antenna, LH2s showed funneling efficiencies close to unity. In contrast, CPs showed lower average funneling efficiencies, greatly varying from molecule to molecule. Cyclodextrin insulation of the conjugated backbone improves EET, increasing the fraction of CPs possessing ɛ = 1. Comparison between LH2s and CPs shows the importance of the protection systems and the protein scaffold of LH2, which keep the chromophores in functional form and at such geometrical arrangement that ensures excellent EET.

  15. Labeling of DOTA-conjugated HPMA-based polymers with trivalent metallic radionuclides for molecular imaging.

    Science.gov (United States)

    Eppard, Elisabeth; de la Fuente, Ana; Mohr, Nicole; Allmeroth, Mareli; Zentel, Rudolf; Miederer, Matthias; Pektor, Stefanie; Rösch, Frank

    2018-02-27

    In this work, the in vitro and in vivo stabilities and the pharmacology of HPMA-made homopolymers were studied by means of radiometal-labeled derivatives. Aiming to identify the fewer amount and the optimal DOTA-linker structure that provides quantitative labeling yields, diverse DOTA-linker systems were conjugated in different amounts to HPMA homopolymers to coordinate trivalent radiometals Me(III)* = gallium-68, scandium-44, and lutetium-177. Short linkers and as low as 1.6% DOTA were enough to obtain labeling yields > 90%. Alkoxy linkers generally exhibited lower labeling yields than alkane analogues despite of similar chain length and DOTA incorporation rate. High stability of the radiolabel in all examined solutions was observed for all conjugates. Labeling with scandium-44 allowed for in vivo PET imaging and ex vivo measurements of organ distribution for up to 24 h. This study confirms the principle applicability of DOTA-HPMA conjugates for labeling with different trivalent metallic radionuclides allowing for diagnosis and therapy.

  16. Conductive and photoactive nature of conjugated polymer based on thiophene functionalized thiazole or benzothiadiazole

    Directory of Open Access Journals (Sweden)

    K. Mahesh

    2018-03-01

    Full Text Available New poly (thiophene vinyl thiazole (PTVT and poly (thiophene vinyl benzothiadiazole (PTVBT was synthesized by Wittig condensation route. The absorption maximum of PTVT and PTVBT appeared at 376 and 410 nm in a solution state, and it was red-shifted to 417 and 510 nm in a thin film state. The optical band gaps were 1.7 and 1.5 eV calculated from thin film absorption edges of the polymer. The photoluminescence spectra of PTVT and PTVBT have an emission peak at 457 nm with bluish green and 487 nm with greenish-yellow fluorescence in THF solution. Both polymers showed a short fluorescence decay time (τ1 of 2.31 and 0.73 ns respectively. Furthermore, the aggregation-caused quenching (ACQ phenomenon observed in both polymers in decreased fluorescence intensity with different water fractions. The lower electrochemical band gaps were achieved for both polymers (1.4, and 1.3 eV from cyclic voltammetry. Both polymers have a granular shaped morphology with good surface roughness was observed using AFM. High thermal stability was observed with 8% weight loss at 400 °C for PTVT and 6% weight loss at 460°C for PTVBT. The highest electrical conductivity was observed from electrochemical impedance measurement which was 7.68·10–6 Ω–1·cm–1 for PTVBT.

  17. A stability study of polymer solar cells using conjugated polymers with different donor or acceptor side chain patterns

    DEFF Research Database (Denmark)

    Heckler, Ilona Maria; Kesters, Jurgen; Defour, Maxime

    2016-01-01

    -phenylethyl group. It is shown that the exchange of the hexyl chain on the DTBT moiety has a negative impact on the stability of the polymer as well as on the performance of the resulting PSCs. On the other hand, partial exchange of the 2-hexyldecyl side chain of the BDT unit by a 2-hydroxyethyl group results......)benzo[c][1,2,5]thiadiazole (DTBT), specifically selected because of its suitability for roll-coating in the ambient environment, is investigated in terms of operational stability via partial exchange (5 or 10%) of the alkyl side chain on either the donor or the acceptor monomer with a 2-hydroxyethyl or 2...

  18. Bulk Heterojunction Solar Cell Devices Prepared with Composites of Conjugated Polymer and Zinc Oxide Nanorods

    Directory of Open Access Journals (Sweden)

    Nguyen Tam Nguyen Truong

    2017-01-01

    Full Text Available ZnO nanorods (Nrods with ~20–50 nm lengths were synthesized using an aqueous solution of zinc acetate and glacial acetic acid. Bulk heterojunction solar cells were fabricated with the structure of indium tin oxide (ITO/polyethylenedioxythiophene doped with polystyrene-sulfonic acid (PEDOT:PSS/ZnO-Nrods + polymer/electron transport layer (ETL/Al. Current density-voltage characterization of the resulting cells showed that, by adding an ETL and using polymers with a low band gap energy, the photoactive layer surface morphology and the device performance can be dramatically improved.

  19. Polymer-drug conjugates: origins, progress to date and future directions.

    Science.gov (United States)

    Kopeček, Jindřich

    2013-01-01

    This overview focuses on bioconjugates of water-soluble polymers with low molecular weight drugs and proteins. After a short discussion of the origins of the field, the state-of-the-art is reviewed. Then research directions needed for the acceleration of the translation of nanomedicines into the clinic are outlined. Two most important directions, synthesis of backbone degradable polymer carriers and drug-free macromolecular therapeutics, a new paradigm in drug delivery, are discussed in detail. Finally, the future perspectives of the field are briefly discussed. Copyright © 2012 Elsevier B.V. All rights reserved.

  20. Precisely Controlled Ultrathin Conjugated Polymer Films for Large Area Transparent Transistors and Highly Sensitive Chemical Sensors.

    Science.gov (United States)

    Khim, Dongyoon; Ryu, Gi-Seong; Park, Won-Tae; Kim, Hyunchul; Lee, Myungwon; Noh, Yong-Young

    2016-04-13

    A uniform ultrathin polymer film is deposited over a large area with molecularlevel precision by the simple wire-wound bar-coating method. The bar-coated ultrathin films not only exhibit high transparency of up to 90% in the visible wavelength range but also high charge carrier mobility with a high degree of percolation through the uniformly covered polymer nanofibrils. They are capable of realizing highly sensitive multigas sensors and represent the first successful report of ethylene detection using a sensor based on organic field-effect transistors. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. BRCAA1 antibody- and Her2 antibody-conjugated amphiphilic polymer engineered CdSe/ZnS quantum dots for targeted imaging of gastric cancer

    Science.gov (United States)

    Li, Chao; Ji, Yang; Wang, Can; Liang, Shujing; Pan, Fei; Zhang, Chunlei; Chen, Feng; Fu, Hualin; Wang, Kan; Cui, Daxiang

    2014-05-01

    Successful development of safe and highly effective nanoprobes for targeted imaging of in vivo early gastric cancer is a great challenge. Herein, we choose the CdSe/ZnS (core-shell) quantum dots (QDs) as prototypical materials, synthesized one kind of a new amphiphilic polymer including dentate-like alkyl chains and multiple carboxyl groups, and then used the prepared amphiphilic polymer to modify QDs. The resultant amphiphilic polymer engineered QDs (PQDs) were conjugated with BRCAA1 and Her2 monoclonal antibody, and prepared BRCAA1 antibody- and Her2 antibody-conjugated QDs were used for in vitro MGC803 cell labeling and in vivo targeted imaging of gastric cancer cells. Results showed that the PQDs exhibited good water solubility, strong photoluminescence (PL) intensity, and good biocompatibility. BRCAA1 antibody- and Her2 antibody-conjugated QD nanoprobes successfully realized targeted imaging of in vivo gastric cancer MGC803 cells. In conclusion, BRCAA1 antibody- and Her2 antibody-conjugated PQDs have great potential in applications such as single cell labeling and in vivo tracking, and targeted imaging and therapeutic effects' evaluation of in vivo early gastric cancer cells in the near future.

  2. The Role of Morphology and Electronic Chain Aggregation on the Optical Gain Properties of Semiconducting Conjugated Polymers

    Science.gov (United States)

    Lampert, Zachary Evan

    Conjugated polymers (CPs) are a novel class of materials that exhibit the optical and electrical properties of semiconductors while still retaining the durability and processability of plastics. CPs are also intrinsically 4-level systems with high luminescence quantum efficiencies making them particularly attractive as organic gain media for solid-state laser applications. However, before CPs can emerge as a commercially available laser technology, a more comprehensive understanding of the morphological dependence of the photophysics is required. In this thesis, the morphology and chain conformation dependence of amplified spontaneous emission (ASE) and optical gain in thin films of poly[2-methoxy-5-(2'-ethylhexyloxy)-p-phenylene vinylene] (MEH-PPV) was investigated. By changing the chemical nature of the solvent from which films were cast, as well as the temperature at which films were annealed, CP films with different morphologies, and hence different degrees of interchain interactions were achieved. Contrary to the common perception that polymer morphology plays a decisive role in determining the ASE behavior of thin CP films, we found that chromophore aggregation and degree of conformational order have minimal impact on optical gain. In fact, experimental results indicated that an extremely large fraction of interchain aggregate species and/or exciton dissociating defects are required to significantly alter the optical properties and suppress stimulated emission. These results are pertinent to the fabrication and optimization of an electrically pumped laser device, as improvements in charge carrier mobility through controlled increases in chain aggregation may provide a viable means of optimizing injection efficiency without significantly degrading optical gain. To offset charge-induced absorption losses under electrical pumping, and to enable the use of more compact and economical sources under optical pumping, conjugated polymers exhibiting low lasing

  3. Micro-structure-mobility correlation in self-organised, conjugated polymer field-effect transistors

    NARCIS (Netherlands)

    Sirringhaus, H.; Brown, P.J.; Friend, R.H.; Nielsen, M.M.; Bechgaard, K.; Langeveld-Voss, B.M.W.; Spiering, A.J.H.; Janssen, R.A.J.; Meijer, E.W.

    2000-01-01

    We have investigated the correlation between polymer microstructure and charge carrier mobility in high-mobility, self-organised field-effect transistors of poly-3-hexyl-thiophene (P3HT). Two different preferential orientations of the microcrystalline P3HT domains with respect to the substrate have

  4. Molecular current modulator consisting of conjugated polymer chain with chemically attached photoactive side groups

    Czech Academy of Sciences Publication Activity Database

    Nešpůrek, Stanislav; Sworakowski, J.

    2001-01-01

    Roč. 393, 1-2 (2001), s. 168-176 ISSN 0040-6090 R&D Projects: GA AV ČR IAA1050901; GA AV ČR KSK4050111 Institutional research plan: CEZ:AV0Z4050913 Keywords : molecular electronics * photoconductivity * polymers Subject RIV: CD - Macromolecular Chemistry Impact factor: 1.266, year: 2001

  5. Conjugated polymer dots for ultra-stable full-color fluorescence patterning.

    Science.gov (United States)

    Chang, Kaiwen; Liu, Zhihe; Chen, Haobin; Sheng, Lan; Zhang, Sean Xiao-An; Chiu, Daniel T; Yin, Shengyan; Wu, Changfeng; Qin, Weiping

    2014-11-12

    Stable full-color fluorescence patterning are achieved by multicolor polymer-dot inks. The fluorescent patterns show extraordinary stability upon various treatments, offering a superior combination of bright fluorescence, excellent photostability, chemical resistance, and eco-friendship. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. Amperometric Analysis of Ru π-Conjugated Polymers: ProspectiveCo-Supports for Enantioselective Ru Catalysts.

    Czech Academy of Sciences Publication Activity Database

    Tito, Duarte Novaes; Klusoň, Petr

    2016-01-01

    Roč. 120, č. 38 (2016), s. 21228-21234 ISSN 1932-7447 R&D Projects: GA ČR(CZ) GA15-04790S Institutional support: RVO:67985858 Keywords : organic photovoltaic cells * sensitized solar- cells * conducting polymers Subject RIV: CI - Industrial Chemistry, Chemical Engineering Impact factor: 4.536, year: 2016

  7. Preparation and in vitro evaluation of polymer conjugates actively targeted using RGD-based peptides

    Czech Academy of Sciences Publication Activity Database

    Böhmová, Eliška; Pola, Robert; Pechar, Michal; Janoušková, Olga; Zuska, K.; Etrych, Tomáš

    2017-01-01

    Roč. 6, 4 (Suppl) (2017), s. 91 ISSN 2325-9604. [International Conference and Exhibition on Nanomedicine and Drug Delivery. 29.05.2017-31.05.2017, Osaka] R&D Projects: GA ČR(CZ) GA16-17207S Institutional support: RVO:61389013 Keywords : polymer drug carriers * HPMA * peptide tumor targeting Subject RIV: CD - Macromolecular Chemistry

  8. Microstructure-mobility correlation in self-organised, conjugated polymer field-effect transistors

    DEFF Research Database (Denmark)

    Sirringhaus, H.; Brown, P.J.; Friend, R.H.

    2000-01-01

    We have investigated the correlation between polymer microstructure and charge carrier mobility in high-mobility, self-organised field-effect transistors of poly-3-hexyl-thiophene (P3HT). Two different preferential orientations of the microcrystalline P3HT domains with respect to the substrate have...

  9. In-situ fabrication of diketopyrrolopyrrole-carbazole-based conjugated polymer/TiO2 heterojunction for enhanced visible light photocatalysis

    Science.gov (United States)

    Yang, Long; Yu, Yuyan; Zhang, Jianling; Chen, Fu; Meng, Xiao; Qiu, Yong; Dan, Yi; Jiang, Long

    2018-03-01

    Aiming at developing highly efficient photocatalysts by broadening the light-harvesting region and suppressing photo-generated electron-hole recombination simultaneously, this work reports rational design and fabrication of donor-acceptor (D-A) conjugated polymer/TiO2 heterojunction catalyst with strong interfacial interactions by a facile in-situ thermal treatment. To expand the light-harvesting window, soluable conjugated copolymers with D-A architecture are prepared by Pd-mediated polycondensation of diketopyrrolopyrrole (DPP) and t-butoxycarbonyl (t-Boc) modified carbazole (Car), and used as visible-light-harvesting antenna to couple with TiO2 nanocrystals. The DPP-Car/TiO2 composites show wide range absorption in 300-1000 nm. To improve the interfacial binding at the interface, a facile in-situ thermal treatment is carried out to cleave the pendant t-Boc groups in carbazole units and liberate the polar amino groups (-NH-) which strongly bind to the surface of TiO2 through dipole-dipole interactions, forming a heterojunction interface. This in-situ thermal treatment changes the surface elemental distribution of TiO2, reinforces the interface bonding at the boundary of conjugated polymers/TiO2 and finally improves the photocatalytic efficiency of DPP-Car/TiO2 under visible-light irradiation. The interface changes are characterized and verified through Fourier-transform infrared spectroscopy (FT-IR), photo images, UV/Vis (solution state and powder diffuse reflection spectroscopy), X-ray powder diffraction (XRD), X-ray photoelectron spectroscopy (XPS), fluorescence, scanning electron microscopy(SEM) and transmission electron microscopy (TEM) techniques. This study provides a new strategy to avoid the low solubility of D-A conjugated polymers and construct highly-efficient conjugated polymer/TiO2 heterojunction by enforcing the interface contact and facilitating charge or energy transfer for the applications in photocatalysis.

  10. A novel polythiophene – ionic liquid modified clay composite solid phase microextraction fiber: Preparation, characterization and application to pesticide analysis

    International Nuclear Information System (INIS)

    Pelit, Füsun Okçu; Pelit, Levent; Dizdaş, Tuğberk Nail; Aftafa, Can; Ertaş, Hasan; Yalçınkaya, E.E.; Türkmen, Hayati; Ertaş, F.N.

    2015-01-01

    Highlights: • A novel polythiophene – ionic liquid modified clay surface has been prepared. • Polymerization was performed electrochemically on a stainless steel wire. • This material was used as a SPME fiber in head space mode. • This new SPME fiber was applied for analysis of pesticides in juice samples. • Fiber adsorption properties were improved by modification of ionic liquids. - Abstract: This report comprises the novel usage of polythiophene – ionic liquid modified clay surfaces for solid phase microextraction (SPME) fiber production to improve the analysis of pesticides in fruit juice samples. Montmorillonite (Mmt) clay intercalated with ionic liquids (IL) was co-deposited with polythiophene (PTh) polymer coated electrochemically on an SPME fiber. The surface of the fibers were characterized by using scanning electron microscopy (SEM). Operational parameters effecting the extraction efficiency namely; the sample volume and pH, adsorption temperature and time, desorption temperature and time, stirring rate and salt amount were optimized. In order to reveal the major effects, these eight factors were selected and Plackett–Burman Design was constructed. The significant parameters detected; adsorption and temperature along with the stirring rate, were further investigated by Box–Behnken design. Under optimized conditions, calibration graphs were plotted and detection limits were calculated in the range of 0.002–0.667 ng mL −1 . Relative standard deviations were no higher than 18%. Overall results have indicated that this novel PTh-IL-Mmt SPME surface developed by the aid of electrochemical deposition could offer a selective and sensitive head space analysis for the selected pesticide residues

  11. A novel polythiophene – ionic liquid modified clay composite solid phase microextraction fiber: Preparation, characterization and application to pesticide analysis

    Energy Technology Data Exchange (ETDEWEB)

    Pelit, Füsun Okçu, E-mail: fusun.okcu@ege.edu.tr; Pelit, Levent; Dizdaş, Tuğberk Nail; Aftafa, Can; Ertaş, Hasan; Yalçınkaya, E.E.; Türkmen, Hayati; Ertaş, F.N.

    2015-02-15

    Highlights: • A novel polythiophene – ionic liquid modified clay surface has been prepared. • Polymerization was performed electrochemically on a stainless steel wire. • This material was used as a SPME fiber in head space mode. • This new SPME fiber was applied for analysis of pesticides in juice samples. • Fiber adsorption properties were improved by modification of ionic liquids. - Abstract: This report comprises the novel usage of polythiophene – ionic liquid modified clay surfaces for solid phase microextraction (SPME) fiber production to improve the analysis of pesticides in fruit juice samples. Montmorillonite (Mmt) clay intercalated with ionic liquids (IL) was co-deposited with polythiophene (PTh) polymer coated electrochemically on an SPME fiber. The surface of the fibers were characterized by using scanning electron microscopy (SEM). Operational parameters effecting the extraction efficiency namely; the sample volume and pH, adsorption temperature and time, desorption temperature and time, stirring rate and salt amount were optimized. In order to reveal the major effects, these eight factors were selected and Plackett–Burman Design was constructed. The significant parameters detected; adsorption and temperature along with the stirring rate, were further investigated by Box–Behnken design. Under optimized conditions, calibration graphs were plotted and detection limits were calculated in the range of 0.002–0.667 ng mL{sup −1}. Relative standard deviations were no higher than 18%. Overall results have indicated that this novel PTh-IL-Mmt SPME surface developed by the aid of electrochemical deposition could offer a selective and sensitive head space analysis for the selected pesticide residues.

  12. Functionalization of silicon nanowires by conductive and non-conductive polymers

    Science.gov (United States)

    Belhousse, S.; Tighilt, F.-Z.; Sam, S.; Lasmi, K.; Hamdani, K.; Tahanout, L.; Megherbi, F.; Gabouze, N.

    2017-11-01

    The work reports on the development of hybrid devices based on silicon nanowires (SiNW) with polymers and the difference obtained when using conductive and non-conductive polymers. SiNW have attracted much attention due to their importance in understanding the fundamental properties at low dimensionality as well as their potential application in nanoscale devices as in field effect transistors, chemical or biological sensors, battery electrodes and photovoltaics. SiNW arrays were formed using metal assisted chemical etching method. This process is simple, fast and allows obtaining a wide range of silicon nanostructures. Hydrogen-passivated SiNW surfaces show relatively poor stability. Surface modification with organic species confers the desired stability and enhances the surface properties. For this reason, this work proposes a covalent grafting of organic material onto SiNW surface. We have chosen a non-conductive polymer polyvinylpyrrolidone (PVP) and conductive polymers polythiophene (PTh) and polypyrrole (PPy), in order to evaluate the electric effect of the polymers on the obtained materials. The hybrid structures were elaborated by the polymerization of the corresponding conjugated monomers by electrochemical route; this electropolymerization offers several advantages such as simplicity and rapidity. SiNW functionalization by conductive polymers has shown to have a huge effect on the electrical mobility. Hybrid surface morphologies were characterized by scanning electron microscopy (SEM), infrared spectroscopy (FTIR-ATR) and contact angle measurements.

  13. Visible-Light-Driven Hydrogen Evolution Using Planarized Conjugated Polymer Photocatalysts.

    Science.gov (United States)

    Sprick, Reiner Sebastian; Bonillo, Baltasar; Clowes, Rob; Guiglion, Pierre; Brownbill, Nick J; Slater, Benjamin J; Blanc, Frédéric; Zwijnenburg, Martijn A; Adams, Dave J; Cooper, Andrew I

    2016-01-26

    Linear poly(p-phenylene)s are modestly active UV photocatalysts for hydrogen production in the presence of a sacrificial electron donor. Introduction of planarized fluorene, carbazole, dibenzo[b,d]thiophene or dibenzo[b,d]thiophene sulfone units greatly enhances the H 2 evolution rate. The most active dibenzo[b,d]thiophene sulfone co-polymer has a UV photocatalytic activity that rivals TiO 2 , but is much more active under visible light. The dibenzo[b,d]thiophene sulfone co-polymer has an apparent quantum yield of 2.3 % at 420 nm, as compared to 0.1 % for platinized commercial pristine carbon nitride.

  14. Biodegradable star HPMA polymer-drug conjugates: biodegradability, distribution and anti-tumor efficacy

    Czech Academy of Sciences Publication Activity Database

    Etrych, Tomáš; Kovář, Lubomír; Strohalm, Jiří; Chytil, Petr; Říhová, Blanka; Ulbrich, Karel

    2011-01-01

    Roč. 154, č. 3 (2011), s. 241-248 ISSN 0168-3659 R&D Projects: GA AV ČR IAA400500806; GA AV ČR IAAX00500803; GA ČR GAP301/11/0325 Institutional research plan: CEZ:AV0Z40500505; CEZ:AV0Z50200510 Keywords : star polymer * HPMA copolymers * drug release Subject RIV: CD - Macromolecular Chemistry Impact factor: 5.732, year: 2011

  15. Electrical properties of .sigma.-conjugated polymers with additives and their applications in sensors

    Czech Academy of Sciences Publication Activity Database

    Nešpůrek, Stanislav; Wang, Geng; Böhm, S.; Kořínek, M.; Adler, H.-J.

    2004-01-01

    Roč. 210, - (2004), s. 513-521 ISSN 1022-1360. [International Symposium on Reactive Polymers in Inhomogeneous Systems, in Melts and at Interfaces /2./. Dresden, 28.09.2003-01.10.2003] R&D Projects: GA MŠk ME 440; GA MŠk OC D14.30 Institutional research plan: CEZ:AV0Z4050913 Keywords : polysilylenes * charge transport * doping Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 0.691, year: 2004

  16. Enzyme-Polymers Conjugated to Quantum-Dots for Sensing Applications

    Directory of Open Access Journals (Sweden)

    Alexandra Mansur

    2011-10-01

    Full Text Available In the present research, the concept of developing a novel system based on polymer-enzyme macromolecules was tested by coupling carboxylic acid functionalized poly(vinyl alcohol (PVA-COOH to glucose oxidase (GOx followed by the bioconjugation with CdS quantum-dots (QD. The resulting organic-inorganic nanohybrids were characterized by UV-visible spectroscopy, infrared spectroscopy, Photoluminescence spectroscopy (PL and transmission electron microscopy (TEM. The spectroscopy results have clearly shown that the polymer-enzyme macromolecules (PVA-COOH/GOx were synthesized by the proposed zero-length linker route. Moreover, they have performed as successful capping agents for the nucleation and constrained growth of CdS quantum-dots via aqueous colloidal chemistry. The TEM images associated with the optical absorption results have indicated the formation of CdS nanocrystals with estimated diameters of about 3.0 nm. The “blue-shift” in the visible absorption spectra and the PL values have provided strong evidence that the fluorescent CdS nanoparticles were produced in the quantum-size confinement regime. Finally, the hybrid system was biochemically assayed by injecting the glucose substrate and detecting the formation of peroxide with the enzyme horseradish peroxidase (HRP. Thus, the polymer-enzyme-QD hybrid has behaved as a nanostructured sensor for glucose detecting.

  17. Cost–effective Polythiophene Counter Electrodes for Dye Sensitized Solar Cells

    Directory of Open Access Journals (Sweden)

    Tolu Merve Celik

    2016-01-01

    Full Text Available Dye sensitized solar cells (DSSCs are most promising devices among third–generation solar cells because of low cost, easy production, environmental friendliness, and relatively high conversion efficiency. Counter electrode (CE, which is an important component in DSSCs, functions as an electron transfer agent as well as the regenerator of redox couple. Hitherto, various methods and materials were used to prepare different counter electrodes.Among these materials, conducting polymers have been widely investigated and employed in various applications such as sensors, supercapacitors, energy storage devices, DSSCs and others. In this study, Polythiophene (PTh conducting polymer was successfully synthesized by electrochemical deposition method, and employed as an alternative to expensive platinum (Pt CE for DSSC. Besides, PTh conducting polymer was electrochemically deposited via cyclic voltammetry method on FTO substrates. The morphology of the PTh film was characterized by SEM and AFM. Finally, the photovoltaic performance of PTh CE based DSSC was compared with PEDOT CE based device. This new concept—along with promising electrocatalytic activity and facile electron transfer—provides a new approach to enhance the photovoltaic performances of Pt–free DSSCs.

  18. Synthesis and Characterization of Novel Polythiophenes Containing Pyrene Chromophores: Thermal, Optical and Electrochemical Properties

    Directory of Open Access Journals (Sweden)

    Bianca X. Valderrama-García

    2016-01-01

    Full Text Available A novel series of pyrene containing thiophene monomers TPM1–5 were synthesized and fully characterized by FTIR, MS, 1H- and 13C-NMR spectroscopy; their thermal properties were determined by TGA and DSC. These monomers were chemically polymerized using FeCl3 as oxidizing agent to give the corresponding oligomers TPO1–5 and they were electrochemically polymerized to obtain the corresponding polymer films deposited onto ITO. All oligomers exhibited good thermal stability, with T10 values between 255 and 299 °C, and Tg values varying from 36 to 39 °C. The monomers showed an absorption band at 345 nm due to the S0 → S2 transition of the pyrene group, whereas the fluorescence spectra showed a broad emission band arising from the “monomer” emission at 375–420 nm. The obtained polymers exhibited two absorption bands at 244 and 354 nm, due to the polythiophene and the pyrene moieties, respectively. The fluorescence spectra of polymers showed a broad “monomer” emission at 380–420 nm followed by an intense excimer emission band at 570 nm, due to the presence of intramolecular pyrene-pyrene interactions in these compounds.

  19. Preparation of nanocrystals and nanocomposites of nanocrystal-conjugated polymer, and their photophysical properties in confined geometries

    Energy Technology Data Exchange (ETDEWEB)

    Xu, Jun [Iowa State Univ., Ames, IA (United States)

    2007-01-01

    Semiconductors nanocrystals (NCs), also called quantum dots (QDs), have attracted tremendous interest over the past decade in the fields of physics, chemistry, and engineering. Due to the quantum-confined nature of QDs, the variation of particle size provides continuous and predictable changes in fluorescence emission. On the other hand, conjugated polymers (CPs) have been extensively studied for two decades due to their semiconductor-like optical and electronic properties. The electron and energy transfer between NCs and CPs occur in solar cells and light emitting diodes (LEDs), respectively. Placing CPs in direct contact with a NC (i.e., preparing NC-CP nanocomposites) carries advantage over cases where NC aggregation dominates. Such NC-CP nanocomposites possess a well-defined interface that significantly promotes the charge or energy transfer between these two components. However, very few studies have centered on such direct integration. We prepared NCs and NC-CP nanocomposites based on heck coupling and investigated the energy and charge transfer between semiconductor NCs (i.e., CdSe QDs), CPs (i.e., poly(3-hexyl thiophene) (P3HT)) in the nanocomposites in confined geometries. Two novel strategies were used to confine NC and/or NC-CP nanocomposites: (a) directly immobilizing nanohybrids, QDs and nanorods in nanoscopic porous alumina membrane (PAM) , and (b) confining the QDs and CPs in sphere-on-flat geometry to induce self-assembly. While investigating the confinement effect, gradient concentric ring patterns of high regularity form spontaneously simply by allowing a droplet of solution containing either conjugated polymer or semiconductor nanocrystal in a consecutive stick-slip mothion in a confined geometry. Such constrained evaporation can be utilized as a simple, cheap, and robust strategy for self-assembling various materials with easily tailored optical and electronic properties into spatially ordered, two-dimensional patterns. These self

  20. Indolo-naphthyridine-6,13-dione Thiophene Building Block for Conjugated Polymer Electronics: Molecular Origin of Ultrahigh n-Type Mobility

    KAUST Repository

    Fallon, Kealan J.

    2016-10-18

    Herein, we present the synthesis and characterization of four conjugated polymers containing a novel chromophore for organic electronics based on an indigoid structure. These polymers exhibit extremely small band gaps of ∼1.2 eV, impressive crystallinity, and extremely high n-type mobility exceeding 3 cm V s. The n-type charge carrier mobility can be correlated with the remarkably high crystallinity along the polymer backbone having a correlation length in excess of 20 nm. Theoretical analysis reveals that the novel polymers have highly rigid nonplanar geometries demonstrating that backbone planarity is not a prerequisite for either narrow band gap materials or ultrahigh mobilities. Furthermore, the variation in backbone crystallinity is dependent on the choice of comonomer. OPV device efficiencies up to 4.1% and charge photogeneration up to 1000 nm are demonstrated, highlighting the potential of this novel chromophore class in high-performance organic electronics.

  1. Indolo-naphthyridine-6,13-dione Thiophene Building Block for Conjugated Polymer Electronics: Molecular Origin of Ultrahigh n-Type Mobility

    KAUST Repository

    Fallon, Kealan J.; Wijeyasinghe, Nilushi; Manley, Eric F.; Dimitrov, Stoichko D.; Yousaf, Syeda A.; Ashraf, Raja S.; Duffy, Warren; Guilbert, Anne A. Y.; Freeman, David M. E.; Al-Hashimi, Mohammed; Nelson, Jenny; Durrant, James R.; Chen, Lin X.; McCulloch, Iain; Marks, Tobin J.; Clarke, Tracey M.; Anthopoulos, Thomas D.; Bronstein, Hugo

    2016-01-01

    Herein, we present the synthesis and characterization of four conjugated polymers containing a novel chromophore for organic electronics based on an indigoid structure. These polymers exhibit extremely small band gaps of ∼1.2 eV, impressive crystallinity, and extremely high n-type mobility exceeding 3 cm V s. The n-type charge carrier mobility can be correlated with the remarkably high crystallinity along the polymer backbone having a correlation length in excess of 20 nm. Theoretical analysis reveals that the novel polymers have highly rigid nonplanar geometries demonstrating that backbone planarity is not a prerequisite for either narrow band gap materials or ultrahigh mobilities. Furthermore, the variation in backbone crystallinity is dependent on the choice of comonomer. OPV device efficiencies up to 4.1% and charge photogeneration up to 1000 nm are demonstrated, highlighting the potential of this novel chromophore class in high-performance organic electronics.

  2. Influence of acceptor on charge mobility in stacked .pi.-conjugated polymers

    Czech Academy of Sciences Publication Activity Database

    Sun, S.-J.; Menšík, Miroslav; Toman, Petr; Gagliardi, A.; Král, Karel

    2018-01-01

    Roč. 501, 14 February (2018), s. 8-14 ISSN 0301-0104 R&D Projects: GA MŠk(CZ) LTC17029; GA ČR(CZ) GA15-05095S EU Projects: European Commission(XE) MPNS COST Action MP1406 Institutional support: RVO:61389013 ; RVO:68378271 Keywords : hole mobility * conductive polymers * P3HT Subject RIV: BM - Solid Matter Physics ; Magnetism; BM - Solid Matter Physics ; Magnetism (FZU-D) OBOR OECD: Condensed matter physics (including formerly solid state physics , supercond.); Condensed matter physics (including formerly solid state physics , supercond.) (FZU-D) Impact factor: 1.767, year: 2016

  3. Theoretical study on naphthobischalcogenadiazole conjugated polymer systems and C61 derivative as organic photovoltaic semiconductors

    Science.gov (United States)

    Fujita, Takehiro; Matsui, Toru; Sumita, Masato; Imamura, Yutaka; Morihashi, Kenji

    2018-02-01

    We investigated the charge-transfer reactions of solar cells including a quaterthiophene copolymer with naphtho-bis-thiadiazole (PNTz4T) and naphtho-bis-oxadiazole (PNOz4T) using constrained density functional theory (CDFT). According to our calculations, the high electron-transfer rate results in a highly efficient solar cell, and the stable charge-transfer state results in low energy loss. Our computations imply that the following three factors are crucial to improve the performance of semiconducting polymers: (i) large structural changes following charge-transfer, (ii) narrow band gap, and (iii) spatially delocalized lowest unoccupied molecular orbital (LUMO) of the ground state.

  4. Emulsion-Based RIR-MAPLE Deposition of Conjugated Polymers: Primary Solvent Effect and Its Implications on Organic Solar Cell Performance.

    Science.gov (United States)

    Ge, Wangyao; Li, Nan K; McCormick, Ryan D; Lichtenberg, Eli; Yingling, Yaroslava G; Stiff-Roberts, Adrienne D

    2016-08-03

    Emulsion-based, resonant infrared matrix-assisted pulsed laser evaporation (RIR-MAPLE) has been demonstrated as an alternative technique to deposit conjugated polymer films for photovoltaic applications; yet, a fundamental understanding of how the emulsion target characteristics translate into film properties and solar cell performance is unclear. Such understanding is crucial to enable the rational improvement of organic solar cell (OSC) efficiency and to realize the expected advantages of emulsion-based RIR-MAPLE for OSC fabrication. In this paper, the effect of the primary solvent used in the emulsion target is studied, both experimentally and theoretically, and it is found to determine the conjugated polymer cluster size in the emulsion as well as surface roughness and internal morphology of resulting polymer films. By using a primary solvent with low solubility-in-water and low vapor pressure, the surface roughness of deposited P3HT and PCPDTBT polymer films was reduced to 10 nm, and the efficiency of P3HT:PC61BM OSCs was increased to 3.2% (∼100 times higher compared to the first MAPLE OSC demonstration [ Caricato , A. P. ; Appl. Phys. Lett. 2012 , 100 , 073306 ]). This work unveils the mechanism of polymer film formation using emulsion-based RIR-MAPLE and provides insight and direction to determine the best ways to take advantage of the emulsion target approach to control film properties for different applications.

  5. Design of PEI-conjugated bio-reducible polymer for efficient gene delivery.

    Science.gov (United States)

    Nam, Joung-Pyo; Kim, Soyoung; Kim, Sung Wan

    2018-07-10

    The poly(cystaminebis(acrylamide)-diaminohexane) (poly(CBA-DAH)) was designed previously as a bio-reducible efficient gene delivery carrier. However, the high weight ratio required to form the polyplexes between poly(CBA-DAH) with pDNA is still a problem that needs to be addressed. To solve this problem and increase the transfection efficiency, poly(ethylenimine) (PEI, 1.8 kDa) was conjugated to poly(CBA-DAH) via disulfide bond. The PEI conjugated poly(CBA-DAH) (PCDP) can bind with pDNA at a very low weight ratio of 0.5 and above, like PEI 25 kDa, and form the polyplexes with nano-size (102-128 nm) and positive surface charge (27-34 mV). PCDP and PCDP polyplexes had negligible cytotoxicity and indicated similar or better cellular uptake than the comparison groups such as PEI 25 kDa and Lipofectamine® polyplexes. To confirm the transfection efficiency, the plasmid DNA (pDNA) encoded with the luciferase reporter gene (gWiz-Luc) and green fluorescent protein reporter gene (GFP) were used and treated with PCDP into the A549, Huh-7, and Mia PaCa-2 cells. PCDP/pDNA polyplexes showed highest transfection efficiency in all tested cell lines. In the luciferase assay, PCDP polyplexes showed 10.2 times higher gene transfection efficiency than Lipofectamine® polyplexes in mimic in vivo conditions (30% FBS, A549 cells). The VEGF siRNA expressing plasmid (pshVEGF), which is constructed as a therapeutic gene by our previous work, was delivered by PCDP into the cancer cells. The VEGF gene expression of PCDP/pshVEGF polyplexes was dramatically lower than control and the VEGF gene silencing efficiencies of PCDP/pshVEGF (w/w; 10/1) polyplexes were 54% (A549 cells), 77% (Huh-7 cells), and 66% (Mia PaCa-2 cells). In addition, PCDP/pshVEGF had reduced cell viability rates of about 31% (A549 cells), 39% (Huh-7 cells), and 42% (Mia PaCa-2 cells) and showed better results than all comparison groups. In the transfection efficiency and VEGF silencing assay, PCDP polyplexes showed

  6. Assessment of Embedded Conjugated Polymer Sensor Arrays for Potential Load Transmission Measurement in Orthopaedic Implants

    Directory of Open Access Journals (Sweden)

    Carolina Micolini

    2017-11-01

    Full Text Available Load transfer through orthopaedic joint implants is poorly understood. The longer-term outcomes of these implants are just starting to be studied, making it imperative to monitor contact loads across the entire joint implant interface to elucidate the force transmission and distribution mechanisms exhibited by these implants in service. This study proposes and demonstrates the design, implementation, and characterization of a 3D-printed smart polymer sensor array using conductive polyaniline (PANI structures embedded within a polymeric parent phase. The piezoresistive characteristics of PANI were investigated to characterize the sensing behaviour inherent to these embedded pressure sensor arrays, including the experimental determination of the stable response of PANI to continuous loading, stability throughout the course of loading and unloading cycles, and finally sensor repeatability and linearity in response to incremental loading cycles. This specially developed multi-material additive manufacturing process for PANI is shown be an attractive approach for the fabrication of implant components having embedded smart-polymer sensors, which could ultimately be employed for the measurement and analysis of joint loads in orthopaedic implants for in vitro testing.

  7. Towards Designing Environmentally Stable Conjugated Polymers with very Small Band-Gaps

    International Nuclear Information System (INIS)

    Hong, Sung Y.; Kim, Sung C.

    2003-01-01

    We have investigated substituent effect on the stabilization energies, and nucleus-independent chemical shifts of pentafulvalenes and on the electronic structures of the corresponding polypentafulvalenes to design environmentally stable semiconductive or conductive polymers. Geometrical optimizations of the molecules were carried out at the density functional level of theory with B3LYP hybrid functional and 6-311+G(d) basis set. Stabilization energies were estimated using isodesmic and homodesmotic reactions. As a criterion of aromaticity nucleus-independent chemical shifts of the molecules were computed using GIAO approach. For the polymers the geometrical parameters were optimized through AM1 band calculations and the electronic structures were obtained through modified extended Huckel band calculations. It is found that strong electronwithdrawing substituents increase isodesmic and homodesmotic stabilization energies of pentafulvalene, though it does not increase the aromaticity. Nitro-substituted pentafulvalene is estimated to have stabilization energy as much as azulene. However, substitution either with electron-donating groups or with electronwithdrawing groups does not significantly affect the electronic structures of polypentafulvalene and poly (vinylenedioxypentafulvalene)

  8. Bulk Heterojunction Solar Cells Based on Blends of Conjugated Polymers with II–VI and IV–VI Inorganic Semiconductor Quantum Dots

    Directory of Open Access Journals (Sweden)

    Ryan Kisslinger

    2017-01-01

    Full Text Available Bulk heterojunction solar cells based on blends of quantum dots and conjugated polymers are a promising configuration for obtaining high-efficiency, cheaply fabricated solution-processed photovoltaic devices. Such devices are of significant interest as they have the potential to leverage the advantages of both types of materials, such as the high mobility, band gap tunability and possibility of multiple exciton generation in quantum dots together with the high mechanical flexibility and large molar extinction coefficient of conjugated polymers. Despite these advantages, the power conversion efficiency (PCE of these hybrid devices has remained relatively low at around 6%, well behind that of all-organic or all-inorganic solar cells. This is attributed to major challenges that still need to be overcome before conjugated polymer–quantum dot blends can be considered viable for commercial application, such as controlling the film morphology and interfacial structure to ensure efficient charge transfer and charge transport. In this work, we present our findings with respect to the recent development of bulk heterojunctions made from conjugated polymer–quantum dot blends, list the ongoing strategies being attempted to improve performance, and highlight the key areas of research that need to be pursued to further develop this technology.

  9. Photochemical half-cells using mixture films of fullerene-ethylenediamine adduct microparticles and polythiophene

    International Nuclear Information System (INIS)

    Akiyama, Tsuyoshi; Oku, Takeo; Matsumura, Satoshi; Matsuoka, Ken-ichi; Yamada, Sunao

    2013-01-01

    In this study, C 60 fullerene–ethylenediamine adduct microparticles were prepared. Mixture films of these microparticles and polythiophene were fabricated on indium–tin-oxide transparent electrodes by spin-coating. Incorporation of C 60 –ethylenediamine microparticles was verified by scanning electron microscopy (SEM) measurements. The coverage values of these microparticles were approximately 3–17%, which were calculated from SEM images of modified electrodes. Fluorescence spectra of modified electrodes indicated that the emission intensity of polythiophene in these mixture films was apparently quenched by these C 60 –ethylenediamine microparticles as compared with a polythiophene film without these microparticles. In the presence of methylviologen, these modified electrodes generated stable photocurrent. The photoexciting species was polythiophene, which was verified by profiles of photocurrent action spectra. The C 60 –ethylenediamine microparticles substantially enhanced the photocurrent signals generated by the polythiophene-modified electrode.

  10. Electroactive subwavelength gratings (ESWGs) from conjugated polymers for color and intensity modulation

    Science.gov (United States)

    Bhuvana, Thiruvelu; Kim, Byeonggwan; Yang, Xu; Shin, Haijin; Kim, Eunkyoung

    2012-05-01

    Subwavelength gratings with electroactive polymers such as poly(3-hexylthiophene) (P3HT) and poly(3,4-propylenedioxythiophene-phenylene) (P(ProDOT-Ph)) controlled the color intensity for various visible colors of diffracted light in a single device. Under the illumination of a white light, at a fixed angle of incidence, the color intensity of the diffracted light was reversibly switched from the maximum value down to 15% (85% decrease) by applying -2 to 2 V due to electrochemical (EC) reaction. All spectral colors including red, green, and blue were generated by changing the angle of incidence, and the intensity of each color was modulated electrochemically at a single EC device. With electroactive subwavelength gratings (ESWGs) of P3HT, the maximum modulation of the color intensity was observed in the red-yellow quadrant in the CIE color plot, whereas for the ESWGs of P(ProDOT-Ph), the maximum modulation of the color intensity was observed in the yellow-green and green-blue quadrants. Both ESWGs showed a memory effect, keeping their color and intensity even after power was turned off for longer than 40 hours.Subwavelength gratings with electroactive polymers such as poly(3-hexylthiophene) (P3HT) and poly(3,4-propylenedioxythiophene-phenylene) (P(ProDOT-Ph)) controlled the color intensity for various visible colors of diffracted light in a single device. Under the illumination of a white light, at a fixed angle of incidence, the color intensity of the diffracted light was reversibly switched from the maximum value down to 15% (85% decrease) by applying -2 to 2 V due to electrochemical (EC) reaction. All spectral colors including red, green, and blue were generated by changing the angle of incidence, and the intensity of each color was modulated electrochemically at a single EC device. With electroactive subwavelength gratings (ESWGs) of P3HT, the maximum modulation of the color intensity was observed in the red-yellow quadrant in the CIE color plot, whereas for the

  11. A molecular dynamic simulation study of mechanical properties of graphene–polythiophene composite with Reax force field

    International Nuclear Information System (INIS)

    Nayebi, Payman; Zaminpayma, Esmaeil

    2016-01-01

    In this paper, we performed molecular dynamic simulations by Reax force field to study the mechanical properties of graphene–polythiophene nanocomposite. By computing elastic constant, breaking stress, breaking strain and Young's modulus from the stress–strain curve for the nanocomposites, we investigated effects of tension orientation, graphene loading to the polymer, temperature of nanocomposite and defect of graphene on these mechanical characters. It is found that mechanical characters of tension along the zigzag orientation are higher than other directions. Also, by increasing the weight concentration of graphene in composite, the Young's modulus and breaking strain increase. Our results showed that the Young's modulus decreased with increasing temperature. Finally by applying defect on graphene structure, we found that one atom missing defect has lower Young's modulus. Also, by increasing the defects concentration, elastic modulus decreases gradually. - Highlights: • We studied mechanical properties of graphene–polythiophene nanocomposite. • Mechanical characters of tension along the zigzag are higher than other directions. • By increasing the weight concentration of graphene in composite, the Young's modulus increases. • Young's modulus decreased with increasing temperature. • By increasing the defects concentration, elastic modulus decreases gradually.

  12. Crafting semiconductor organic-inorganic nanocomposites via placing conjugated polymers in intimate contact with nanocrystals for hybrid solar cells

    Energy Technology Data Exchange (ETDEWEB)

    Zhao, Lei; Lin, Zhiqun [School of Materials Science and Engineering, Georgia Institute of Technology, Atlanta, GA (United States)

    2012-08-22

    Semiconductor organic-inorganic hybrid solar cells incorporating conjugated polymers (CPs) and nanocrystals (NCs) offer the potential to deliver efficient energy conversion with low-cost fabrication. The CP-based photovoltaic devices are complimented by an extensive set of advantageous characteristics from CPs and NCs, such as lightweight, flexibility, and solution-processability of CPs, combined with high electron mobility and size-dependent optical properties of NCs. Recent research has witnessed rapid advances in an emerging field of directly tethering CPs on the NC surface to yield an intimately contacted CP-NC nanocomposite possessing a well-defined interface that markedly promotes the dispersion of NCs within the CP matrix, facilitates the photoinduced charge transfer between these two semiconductor components, and provides an effective platform for studying the interfacial charge separation and transport. In this Review, we aim to highlight the recent developments in CP-NC nanocomposite materials, critically examine the viable preparative strategies geared to craft intimate CP-NC nanocomposites and their photovoltaic performance in hybrid solar cells, and finally provide an outlook for future directions of this extraordinarily rich field. (Copyright copyright 2012 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  13. Unified picture of the photoexcitations in phenylene-based conjugated polymers: Universal spectral and dynamical features in subpicosecond transient absorption

    International Nuclear Information System (INIS)

    Kraabel, B.; Klimov, V. I.; Kohlman, R.; Xu, S.; Wang, H-L.; McBranch, D. W.

    2000-01-01

    Using subpicosecond transient absorption spectroscopy, we investigate the primary photoexcitations in thin films and solutions of several phenylene-based conjugated polymers and an oligomer. We identify several features in the transient absorption spectra and dynamics that are common to all of the materials which we studied from this family. The first spectral feature is a photoinduced absorption (PA) band peaking near 1 eV that has intensity-dependent dynamics that match the stimulated emission dynamics exactly over two orders of magnitude in excitation density. This band is associated with singlet intrachain excitons. The second spectral feature (observed only in thin films and aggregated solutions) is a PA band peaking near 1.8 eV, that is longer lived than the 1 eV exciton PA band, and that has dynamics that are independent (or weakly dependent) on excitation density. This feature is attributed to polarons, generated through a mechanism that is sample dependent. In pristine samples, polarons are generated via a mechanism that is quadratic in exciton density, whereas in photodegraded samples or samples doped with electron acceptors, the generation mechanism becomes linear in exciton density. (c) 2000 The American Physical Society

  14. Combined polymer-curcumin conjugate and ependymal progenitor/stem cell treatment enhances spinal cord injury functional recovery.

    Science.gov (United States)

    Requejo-Aguilar, Raquel; Alastrue-Agudo, Ana; Cases-Villar, Marta; Lopez-Mocholi, Eric; England, Richard; Vicent, María J; Moreno-Manzano, Victoria

    2017-01-01

    Spinal cord injury (SCI) suffers from a lack of effective therapeutic strategies. Animal models of acute SCI have provided evidence that transplantation of ependymal stem/progenitor cells of the spinal cord (epSPCs) induces functional recovery, while systemic administration of the anti-inflammatory curcumin provides neuroprotection. However, functional recovery from chronic stage SCI requires additional enhancements in available therapeutic strategies. Herein, we report on a combination treatment for SCI using epSPCs and a pH-responsive polymer-curcumin conjugate. The incorporation of curcumin in a pH-responsive polymeric carrier mainchain, a polyacetal (PA), enhances blood bioavailability, stability, and provides a means for highly localized delivery. We find that PA-curcumin enhances neuroprotection, increases axonal growth, and can improve functional recovery in acute SCI. However, when combined with epSPCs, PA-curcumin also enhances functional recovery in a rodent model of chronic SCI. This suggests that combination therapy may be an exciting new therapeutic option for the treatment of chronic SCI in humans. Copyright © 2016 Elsevier Ltd. All rights reserved.

  15. Ultra-fast relaxation, decoherence, and localization of photoexcited states in π-conjugated polymers

    Science.gov (United States)

    Mannouch, Jonathan R.; Barford, William; Al-Assam, Sarah

    2018-01-01

    The exciton relaxation dynamics of photoexcited electronic states in poly(p-phenylenevinylene) are theoretically investigated within a coarse-grained model, in which both the exciton and nuclear degrees of freedom are treated quantum mechanically. The Frenkel-Holstein Hamiltonian is used to describe the strong exciton-phonon coupling present in the system, while external damping of the internal nuclear degrees of freedom is accounted for by a Lindblad master equation. Numerically, the dynamics are computed using the time evolving block decimation and quantum jump trajectory techniques. The values of the model parameters physically relevant to polymer systems naturally lead to a separation of time scales, with the ultra-fast dynamics corresponding to energy transfer from the exciton to the internal phonon modes (i.e., the C-C bond oscillations), while the longer time dynamics correspond to damping of these phonon modes by the external dissipation. Associated with these time scales, we investigate the following processes that are indicative of the system relaxing onto the emissive chromophores of the polymer: (1) Exciton-polaron formation occurs on an ultra-fast time scale, with the associated exciton-phonon correlations present within half a vibrational time period of the C-C bond oscillations. (2) Exciton decoherence is driven by the decay in the vibrational overlaps associated with exciton-polaron formation, occurring on the same time scale. (3) Exciton density localization is driven by the external dissipation, arising from "wavefunction collapse" occurring as a result of the system-environment interactions. Finally, we show how fluorescence anisotropy measurements can be used to investigate the exciton decoherence process during the relaxation dynamics.

  16. Surface and Interface Engineering of Conjugated Polymers and Nanomaterials in Applications of Supercapacitors and Surface-functionalization

    KAUST Repository

    Hou, Yuanfang

    2016-05-23

    In this dissertation, three aspects about surface and interface engineering of conjugated polymers and nanomaterials will be discussed. (i) There is a significant promise for electroactive conjugated polymers (ECPs) in applications of electrochemical devices including energy harvesting, electrochromic displays, etc. Among these, ECPs has also been developed as electroactive materials in electrochemical supercapacitors (ESCs). Compared with metal oxides, ECPs are attractive because they have good intrinsic conductivity, low band-gaps, relatively fast doping-and-undoping process, the ease of synthesis, and tunable electronic and structural properties through structural modifications. Here, Multiple-branch-chain 3,4-ethylenedioxythiophene (EDOT) derivatives was designed as crosslinkers in the co-electropolymerization of EDOT to optimize its morphology and improve the cycling stability of PEDOT in the supercapacitor applications. High-surface-area π-conjugated polymeric networks can be synthesized via the electrochemical copolymerization of the 2D (trivalent) motifs benzo[1,2-b:3,4-b’:5,6-b’’]trithiophene (BTT) and tris-EDOT-benzo[1,2-b:3,4-b’:5,6-b’’]trithiophene (TEBTT) with EDOT. Of all the material systems studied, P(TEBTT/EDOT)-based frameworks achieved the highest areal capacitance with values as high as 443.8 mF cm-2 (at 1 mA cm-2), higher than those achieved by the respective homopolymers (PTEBTT and PEDOT) in the same experimental conditions of electrodeposition (PTEBTT: 271.1 mF cm-2 (at 1 mA cm-2); PEDOT: 12.1 mF cm-2 (at 1 mA cm-2). (ii) In electrochemical process, the suitable choice of appropriate electrolytes to enlarge the safe working potential window with electrolyte stability is well known to improve ECPs’ performance in ESCs applications. Ionic liquids (ILs) are ion-composed salts and usually fluid within a wide temperature range with low melting points. There are many unique characteristics for these intrinsic ion conductors

  17. Photodynamic inactivation of bacteria using polyethylenimine-chlorin(e6) conjugates: Effect of polymer molecular weight, substitution ratio of chlorin(e6) and pH.

    Science.gov (United States)

    Huang, Liyi; Zhiyentayev, Timur; Xuan, Yi; Azhibek, Dulat; Kharkwal, Gitika B; Hamblin, Michael R

    2011-04-01

    Antimicrobial photodynamic therapy (APDT) is a novel technique to treat local infections. Previously we reported that the attachment of chlorin(e6) to polyethylenimine (PEI) polymers to form PEI-ce6 conjugates is an effective way to improve ce6 PDT activity against bacteria. The aim of this work was to explore how the polymer molecular weight, substitution ratio (SR) of ce6 and pH value affect the PDT efficacy. We have synthesized PEI-ce6(10) (MW = 60,000, SR = 1) and PEI-ce6(11) (MW = 60,000, SR = 5) and compared these with the previous PEI-ce6(9) (MW = 10,000, SR = 1). We tested the PDT efficacy of these three conjugates against Gram-negative E. coli and Gram-positive bacteria (S. aureus and E. fecalis) at three different pH values (5.0, 7.4, 10.0) that may affect the charge on both the bacterial cells and on the conjugate (that has both basic and acidic groups). PEI-ce6(9) and PEI-ce6(10) were the most effective against these tested bacteria. The PDT effect of all three conjugates depended on pH values. The effective order was pH = 10.0 > pH = 7.4 > pH = 5.0 on E. coli. For S. aureus and E. fecalis the order was pH = 5.0 > pH = 10.0 > pH = 7.4. PEI-ce6(11) PDT activity was worse than PEI-ce6(10) activity which is probably connected to the fact that ce6 molecules are self-quenched within the PEI-ce6(11) molecule. Ce6 quenching within the PEI-ce6 molecules was proved by analyzing fluorescence spectra of PEI-ce6 conjugates at different pH values. There were no differences in bacterial uptake between different pH values in three PEI-ce6 conjugates. We assume high pH (rather than low pH as was hypothesized) disaggregates the conjugates, so the higher pH was more effective than the lower pH against E. coli. But for Gram-positive bacteria, low pH was more effective possibly due to more overall positive charge on the conjugate. Copyright © 2011 Wiley-Liss, Inc.

  18. The effect of changes in π-conjugated terthienyl systems using thienyl and ethylenedioxybenzene functionalized thieno[3,4-b]pyrazine precursors: Multicolored low band gap polymers

    International Nuclear Information System (INIS)

    Tarkuc, Simge; Unver, Elif Kose; Udum, Yasemin Arslan; Tanyeli, Cihangir; Toppare, Levent

    2010-01-01

    New classes of thieno[3,4-b]pyrazines containing thienyl and ethylenedioxy phenyl units on electron-withdrawing moieties of π-conjugated terthienyl were synthesized. The effect of structural differences on electrochemical and optoelectronic properties of the resulting polymers was investigated. Changes in the electronic nature of the functional groups enable to tune the electrochemical properties of the π-conjugated terthienyl monomers by lowering oxidation potential from 0.62 V (DTTP) to 0.56 V (DBTP). Spectroelectrochemical analyses revealed that the neutral polymer (PDBTP) is dark green in its neutral state revealing π-π* transitions in two well-separated bands at 410 and 751 nm. The electronic band gap of polymer, defined as the onset of the π-π* transition, is found to be 1.0 eV. Using the thienyl unit instead of ethylenedioxy phenyl, a red shift in the band gap (0.95 eV) is observed. The polymer, PDTTP, exhibits multicolor electrochromism and can be switched between a dark yellow neutral state, a green intermediate state, and a brown oxidized state. PDBTP also shows a multicolored electrochromic behavior with three distinct states: dark green at the neutral state, a brown intermediate state, and a brown-violet oxidized state.

  19. Preparation of conjugated polymer-based composite thin film for application in solar cell

    International Nuclear Information System (INIS)

    Yu, Yang-Yen; Chien, Wen-Chen; Ko, Yu-Hsin; Chen, Chih-Ping; Chang, Chao-Ching

    2015-01-01

    This paper reports on the enhanced cell efficiency of structures and properties of regioregular poly(3-hexylthiophene) (P3HT)/multiwalled carbon nanotube (MWNT) hybrid materials. The prepared hybrid materials were characterized using ultraviolet–visible absorption spectroscopy, photoluminescence spectroscopy, Fourier transform infrared spectroscopy, X-ray diffraction, scanning electron microscopy, and transmission electron microscopy. Different concentrations of these MWNTs were suspended in polymer solutions and spin-cast onto indium tin oxide (ITO) glass. Solar cells with a device structure of ITO/poly(3,4-ethylenedioxythiophene):poly(4-styrenesulfonate) /P3HT:MWNTs/aluminum were then produced using evaporated aluminum as the back contact. The results showed that the ratio of P3HT to MWNTs considerably influenced the performance of the fabricated solar cells. The efficiency of the solar cells increased with the ratio of carbon nanotubes. Monochromatic incident photon-to-electron conversion efficiency analysis was performed and the results indicated that at the optimal P3HT/MWNTs ratio (= 1/1), the solar cells demonstrated a high-quality conversion of 2.16% with a fill factor of 42.22%, an open circuit voltage of 0.56 V, and a short circuit current of 9.12 mA/cm 2 . - Highlights: • Solar cells ITO/PEDOT:PSS(DMSO)/P3HT:MWNT/Al were fabricated. • Optimal ratio of P3HT to MWNT was investigated. • Solar cell with 2.16% efficiency was obtained

  20. Inverse gold photonic crystals and conjugated polymer coated opals for functional materials

    Energy Technology Data Exchange (ETDEWEB)

    Landon, P.B.; Gutierrez, Jose; Ferraris, John P.; Martinez, I.L.; Giridharagopal, Rajiv; Wu, Y.-C.; Lee, Sergey; Parikh, Kunjal; Gillespie, Jessica; Ussery, Geoffrey; Karimi, Behzad; Baughman, Ray; Zakhidov, Anvar; Glosser, R

    2003-10-01

    Inverse gold photonic crystals templated from synthetic opals with a face centered cubic (FCC) crystal lattice were constructed by heat converting gold chloride to metallic gold. Tetrahedral formations constructed of alternating large and small octahedrons oriented in the zinc sulfide structure were created by controlling the infiltration of gold chloride. Silica spheres were coated with polyanilinesulfonic acid, polypyrrole, poly[2-methoxy-5-(2'-ethylhexyloxy)-1,4-phenylenevinylene] (MEH-PPV) and 5 nm colloidal gold. Ordinary yeast cells were coated with polyanilinesulfonic acid, polypyrrole and 5 nm colloidal gold. Spheres coated with MEH-PPV were dispersed in H{sub 2}O and coated with polyelectrolytes which recharged and sterically stabilized the colloidal surfaces. The recharged spheres self-assembled by sedimentation with a FCC crystalline lattice possessing 500 {mu}m wide and 1 mm long crystallites. Silica spheres with diameters as large as 1500 {mu}m were self-assembled along the [1 0 0] direction of the FCC crystal lattice. Opals infiltrated with gold and opals constructed from polymer coated spheres were co-infiltrated with polypropylene yielding inverse polypropylene composite photonic crystals.

  1. Preparation of conjugated polymer-based composite thin film for application in solar cell

    Energy Technology Data Exchange (ETDEWEB)

    Yu, Yang-Yen, E-mail: yyyu@mail.mcut.edu.tw [Department of Materials Engineering, Ming Chi University of Technology, 84 Gunjuan Road, Taishan, New Taipei City 243, Taiwan (China); Battery Research Center of Green Energy, Ming Chi University of Technology, 84 Gunjuan Road, Taishan, New Taipei City 243, Taiwan (China); Center for Thin Film Technologies and Applications, Ming Chi University of Technology, 84 Gunjuan Road, Taishan, New Taipei City 243, Taiwan (China); Chien, Wen-Chen [Department of Chemical Engineering, Ming Chi University of Technology, 84 Gunjuan Road, Taishan, New Taipei City 243, Taiwan (China); Battery Research Center of Green Energy, Ming Chi University of Technology, 84 Gunjuan Road, Taishan, New Taipei City 243, Taiwan (China); Ko, Yu-Hsin [Department of Materials Engineering, Ming Chi University of Technology, 84 Gunjuan Road, Taishan, New Taipei City 243, Taiwan (China); Chen, Chih-Ping [Department of Materials Engineering, Ming Chi University of Technology, 84 Gunjuan Road, Taishan, New Taipei City 243, Taiwan (China); Battery Research Center of Green Energy, Ming Chi University of Technology, 84 Gunjuan Road, Taishan, New Taipei City 243, Taiwan (China); Chang, Chao-Ching [Department of Chemical and Materials Engineering, Tamkang University, 151, Yingzhuan Rd., Tamsui Dist., New Taipei City 25137, Taiwan (China)

    2015-06-01

    This paper reports on the enhanced cell efficiency of structures and properties of regioregular poly(3-hexylthiophene) (P3HT)/multiwalled carbon nanotube (MWNT) hybrid materials. The prepared hybrid materials were characterized using ultraviolet–visible absorption spectroscopy, photoluminescence spectroscopy, Fourier transform infrared spectroscopy, X-ray diffraction, scanning electron microscopy, and transmission electron microscopy. Different concentrations of these MWNTs were suspended in polymer solutions and spin-cast onto indium tin oxide (ITO) glass. Solar cells with a device structure of ITO/poly(3,4-ethylenedioxythiophene):poly(4-styrenesulfonate) /P3HT:MWNTs/aluminum were then produced using evaporated aluminum as the back contact. The results showed that the ratio of P3HT to MWNTs considerably influenced the performance of the fabricated solar cells. The efficiency of the solar cells increased with the ratio of carbon nanotubes. Monochromatic incident photon-to-electron conversion efficiency analysis was performed and the results indicated that at the optimal P3HT/MWNTs ratio (= 1/1), the solar cells demonstrated a high-quality conversion of 2.16% with a fill factor of 42.22%, an open circuit voltage of 0.56 V, and a short circuit current of 9.12 mA/cm{sup 2}. - Highlights: • Solar cells ITO/PEDOT:PSS(DMSO)/P3HT:MWNT/Al were fabricated. • Optimal ratio of P3HT to MWNT was investigated. • Solar cell with 2.16% efficiency was obtained.

  2. Ultrafast photo-induced nuclear relaxation of a conformationally disordered conjugated polymer probed with transient absorption and femtosecond stimulated Raman spectroscopies

    Energy Technology Data Exchange (ETDEWEB)

    Yu, Wenjian; Donohoo-Vallett, Paul J.; Zhou, Jiawang; Bragg, Arthur E., E-mail: artbragg@jhu.edu [Department of Chemistry, Johns Hopkins University, 3400 N. Charles St., Baltimore, Maryland 21218 (United States)

    2014-07-28

    A combination of transient absorption (TAS) and femtosecond stimulated Raman (FSRS) spectroscopies were used to interrogate the photo-induced nuclear relaxation dynamics of poly(3-cyclohexyl,4-methylthiophene) (PCMT). The large difference in inter-ring dihedral angles of ground and excited-state PCMT make it an ideal candidate for studying large-amplitude vibrational relaxation associated with exciton trapping. Spectral shifting in the S{sub 1} TA spectra on sub-ps timescales (110 ± 20 and 800 ± 100 fs) is similar to spectroscopic signatures of excited-state relaxation observed with related photoexcited conjugated polymers and which have been attributed to exciton localization and a combination of resonant energy transfer and torsional relaxation, respectively. Measurements made with both techniques reveal fast PCMT S{sub 1} decay and triplet formation (τ{sub S1} = 25–32 ps), which is similar to the excited-state dynamics of short oligothiophenes and highly twisted polyconjugated molecules. On ultrafast timescales FSRS of S{sub 1} PCMT offers a new perspective on the nuclear dynamics that underlie localization of excitons in photoexcited conjugated polymers: Spectral dynamics in the C=C stretching region (1400–1600 cm{sup −1}) include a red-shift of the in-phase C=C stretching frequency, as well as a change in the relative intensity of in-phase and out-of-phase stretch intensities on a timescale of ∼100 fs. Both changes indicate an ultrafast vibrational distortion that increases the conjugation length in the region of the localized excitation and are consistent with exciton self-localization or trapping. Wavelength-dependent excited-state FSRS measurements further demonstrate that the C=C stretching frequency provides a useful spectroscopic handle for interrogating the degree of delocalization in excited conjugated polymers given the selectivity achieved via resonance enhancement.

  3. High operational and environmental stability of high-mobility conjugated polymer field-effect transistors through the use of molecular additives

    KAUST Repository

    Nikolka, Mark; Nasrallah, Iyad; Rose, Bradley Daniel; Ravva, Mahesh Kumar; Broch, Katharina; Sadhanala, Aditya; Harkin, David; Charmet, Jerome; Hurhangee, Michael; Brown, Adam; Illig, Steffen; Too, Patrick; Jongman, Jan; McCulloch, Iain; Bredas, Jean-Luc; Sirringhaus, Henning

    2016-01-01

    Due to their low-temperature processing properties and inherent mechanical flexibility, conjugated polymer field-effect transistors (FETs) are promising candidates for enabling flexible electronic circuits and displays. Much progress has been made on materials performance; however, there remain significant concerns about operational and environmental stability, particularly in the context of applications that require a very high level of threshold voltage stability, such as active-matrix addressing of organic light-emitting diode displays. Here, we investigate the physical mechanisms behind operational and environmental degradation of high-mobility, p-type polymer FETs and demonstrate an effective route to improve device stability. We show that water incorporated in nanometre-sized voids within the polymer microstructure is the key factor in charge trapping and device degradation. By inserting molecular additives that displace water from these voids, it is possible to increase the stability as well as uniformity to a high level sufficient for demanding industrial applications.

  4. High operational and environmental stability of high-mobility conjugated polymer field-effect transistors through the use of molecular additives

    KAUST Repository

    Nikolka, Mark

    2016-12-12

    Due to their low-temperature processing properties and inherent mechanical flexibility, conjugated polymer field-effect transistors (FETs) are promising candidates for enabling flexible electronic circuits and displays. Much progress has been made on materials performance; however, there remain significant concerns about operational and environmental stability, particularly in the context of applications that require a very high level of threshold voltage stability, such as active-matrix addressing of organic light-emitting diode displays. Here, we investigate the physical mechanisms behind operational and environmental degradation of high-mobility, p-type polymer FETs and demonstrate an effective route to improve device stability. We show that water incorporated in nanometre-sized voids within the polymer microstructure is the key factor in charge trapping and device degradation. By inserting molecular additives that displace water from these voids, it is possible to increase the stability as well as uniformity to a high level sufficient for demanding industrial applications.

  5. Photoluminescence and solid state properties of rigid pi- conjugated polymers with applications to LED: Alkyl- substituted p-phenyleneethynylene polymers and triblock copolymers

    Science.gov (United States)

    Huang, Wen-Yao

    A series of substituted poly(p-phenyleneethynylene)s, PPE, were synthesized by alkyne metathesis. The substituents dibutyl (a), dioctyl (b), ditetradecyl (c), di-2-ethylhexyl (d) and di-2-cyclohexylethyl; (e)were placed on the 2,5 positions of the phenyl rings. X-ray diffraction studies indicated that the main chains of each polymer were arranged in regular, layered arrays. Liquid crystalline structures were observed by polarized optical microscopy in PPE 4b, 4c and 4d. The temperatures of isotropization of the liquid crystalline structures coincided with the disordering temperatures determined by differential scanning calorimetry. The UV absorption spectra showed a gradual blue shift of the λmax for all these polymers, suggesting a decrease in the electronic delocalization along the chain as the size and geometry of the side group changed. The photoluminescence spectra in dilute toluene solutions are consistent with vibronic coupling and emission from localized excited states. The emission spectra of thin films show characteristics typical of excimer or aggregate formation in the solid state. Lastly, an improved method of molecular weight determination by end group analysis was devised. Molecular organization and orientation in thin films (~100 nm) of a triblock copolymer, PPEPEG, was studied. The morphology of the thin film can be visualized as consisting of PMMA as the major phase in which domains of vertically oriented triblock copolymers are dispersed with PEG groups facing the air-film interface. The molecular and supramolecular structure of a series of well-defined fully conjugated poly(2,5- diakyl-p-phenyleneethynylene)s, PPE, in toluene has been studied in the sol state and in the gel state by surface tension and photoluminescence measurements. Poly (2,6[4- phenyl quinoline]), I, and poly (2,6[p-phenylene] 4- phenyl quinoline), II, were synthesized by the self- condensation of 5-acetyl-2-aminobezophenone and 4-amino- 4 '-acetyl-3-benzoyl biphenyl

  6. Organic Photovoltaic Devices Based on Oriented n-Type Molecular Films Deposited on Oriented Polythiophene Films.

    Science.gov (United States)

    Mizokuro, Toshiko; Tanigaki, Nobutaka; Miyadera, Tetsuhiko; Shibata, Yousei; Koganezawa, Tomoyuki

    2018-04-01

    The molecular orientation of π-conjugated molecules has been reported to significantly affect the performance of organic photovoltaic devices (OPVs) based on molecular films. Hence, the control of molecular orientation is a key issue toward the improvement of OPV performance. In this research, oriented thin films of an n-type molecule, 3,4,9,10-Perylenetetracarboxylic Bisbenzimida-zole (PTCBI), were formed by deposition on in-plane oriented polythiophene (PT) films. Orientation of the PTCBI films was evaluated by polarized UV-vis spectroscopy and 2D-Grazing incidence X-ray diffraction. Results indicated that PTCBI molecules on PT film exhibit nearly edge-on and in-plane orientation (with molecular long axis along the substrate), whereas PTCBI molecules without PT film exhibit neither. OPVs composed of PTCBI molecular film with and without PT were fabricated and evaluated for correlation of orientation with performance. The OPVs composed of PTCBI film with PT showed higher power conversion efficiency (PCE) than that of film without PT. The experiment indicated that in-plane orientation of PTCBI molecules absorbs incident light more efficiently, leading to increase in PCE.

  7. Synthesis of Conjugated Small Molecules and Polymers by a Palladium Catalyzed Cyclopentannulation Strategy: Towards New Organic Semiconductors

    Science.gov (United States)

    Bheemireddy, Sambasiva Reddy

    The utility of conjugated small molecules and polymers as organic semiconductors have seen a tremendous growth in research and development in academia as well as industry because of their processability and flexibility advantages in comparison to inorganic semiconductors. The extensive research over the years has produced a large number of p-type (hole conducting) and n-type (electron conducting) semiconductors that can be used to construct organic electronic devices. Of these materials, p-type semiconductors are more established and extensively studied because of the ease of preparation as well as their better general stability in comparison to n-type materials. Despite recent research into the development of n-type materials, fullerene (C60 and C 70) and its derivatives are still the predominant materials used as electron acceptors for OPV applications. By taking advantage of the electron accepting behavior of cyclopenta[hi]aceanthrylene fragment of C70, we have designed and synthesized new materials based on cyclopenta-fused polycyclic aromatic hydrocarbons (CP-PAHs). By using a newly developed palladium catalyzed cyclopentannulation methodology, 1,2,6,7- tetraarylcyclopenta[hi]aceanthrylenes were prepared by treating diarylethynylenes with 9,10-dibromoanthracene. Scholl cyclodehydrogenation was used to close the externally fused aryl groups to provide access to contorted 2,7,13,18- tetraalkoxytetrabenzo[f,h,r,t]rubicenes. The contortion provides access to more soluble materials than their planar counterparts but still ii allows significant pi-pi stacking between molecules. Using a modified palladium catalyzed cyclopentannulation polymerization followed by a cyclodehydrogenation reaction, a nonconventional synthesis of CP-PAH embedded ladder polymers was also achieved. These ladder polymers possess broad UV-Vis absorptions and narrow optical gaps of 1.17-1.29 eV. The synthesis of new donor-acceptor copolymers incorporating electron accepting 1,2,6,7- tetra(4

  8. Synthesis, characterization and nano-structuration of poly-thiophene derivatives for organic photovoltaic solar cells

    International Nuclear Information System (INIS)

    Berson, S.

    2007-10-01

    This work is devoted to the synthesis of poly-thiophene derivatives with low bandgap and preserving high oxidation potential. Disubstituted thiophenes and 'Donor-Acceptor' bi-thiophenes were synthesized and then polymerized. The side chains of these polymers, donor or acceptor, were modified in order to tune the properties of material as well from the optical point of view as electrochemical. These polymers were also tested in blend with PCBM in bulk-heterojunction photovoltaic cells. Voc delivered by the devices showed a linear dependence according to the potential of oxidation of the polymers. Copolymers containing cyano-thiophene and alkyl- or alkoxy-thiophene showed values of 0.8 V. However, in spite of power conversion efficiency of 1 %, these performances remain lower than the one obtained with the P3HT. Optimizations in terms of morphology are certainly necessary. Indeed, the morphology of the active layer plays a key role in obtaining high power conversion efficiency. An original technique of nano-structuration of the polymer on a nano-metric scale was developed during this work, leading to the development of fibrillar P3HT. These nano-structures, presenting an important degree of order, are formed spontaneously in solution. Their rate compared to amorphous material is perfectly controllable and adjustable in solution and in solid state. Measurements of mobilities show a strong improvement of the transport of load within these fibrillar layers compared to a traditional film of P3HT obtained without annealing. Power conversion efficiencies of 3.6% on glass and 3.3 % on plastic were reached without annealing. (author)

  9. Synthesis, characterization and nano-structuration of poly-thiophene derivatives for organic photovoltaic solar cells

    International Nuclear Information System (INIS)

    Berson, S.

    2007-10-01

    This work is devoted to the synthesis of poly-thiophene derivatives with low bandgap and preserving high oxidation potential. Di-substituted thiophenes and 'Donor-Acceptor' bi-thiophenes were synthesized and then polymerized. The side chains of these polymers, donor or acceptor, were modified in order to tune the properties of material as well from the optical point of view as electrochemical. These polymers were also tested in blend with PCBM in bulk-heterojunction photovoltaic cells. Voc delivered by the devices showed a linear dependence according to the potential of oxidation of the polymers. Copolymers containing cyano-thiophene and alkyl- or alkoxy-thiophene showed values of 0.8 V. However, in spite of power conversion efficiency of 1 %, these performances remain lower than the one obtained with the P3HT. Optimizations in terms of morphology are certainly necessary. Indeed, the morphology of the active layer plays a key role in obtaining high power conversion efficiency. An original technique of nano-structuration of the polymer on a nano-metric scale was developed during this work, leading to the development of fibrillary P3HT. These nano-structures, presenting an important degree of order, are formed spontaneously in solution. Their rate compared to amorphous material is perfectly controllable and adjustable in solution and in solid state. Measurements of mobilities show a strong improvement of the transport of load within these fibrillary layers compared to a traditional film of P3HT obtained without annealing. Power conversion efficiencies of 3.6 % on glass and 3.3 % on plastic were reached without annealing. (author)

  10. Polythiophenes and fullerene derivatives based donor-acceptor system: topography by atomic force microscopy

    International Nuclear Information System (INIS)

    Marcakova, M. L.; Repovsky, D.; Cik, G.; Velic, D.

    2017-01-01

    The goal of this work is to examine the surface of a polythiophene/fullerene film in order to understand the structure. In this work polythiophene is used as electron donor and fullerene-derivative is used as electron acceptor. Atomic force microscopy (AFM), is an ideal method to study surfaces and nanostructures. Surfaces of fullerene C60 , fullerene-derivates PCBM, polythiophene P12 and a mixture of P12 and PCBM are characterized. In all samples, the average roughness, the arithmetical value of divergence from the high of the surface, is determined concluding that P12 and PCBM mix together well and form a film with specific topography. (authors)

  11. Polythiophene nanocomposites as high performance electrode material for supercapacitor application

    Science.gov (United States)

    Vijeth, H.; Niranjana, M.; Yesappa, L.; Ashokkumar, S. P.; Devendrappa, H.

    2018-04-01

    A polythiophene-aluminium oxide nanocomposite is prepared by in situ chemical polymerisation in presence of anionic surfactant camphor sulfonic acid (CSA). The characterisation of nano composite was done by X-ray Diffraction (XRD), surface morphology was studied using Atomic Force Microscopy (AFM). The electrochemical performance is evaluated using cyclic voltammetry in 1M H2SO4. As an electroactive material, it exhibits high specific capacitance of 654.5 and 757 F/g for PTH and PTHA nanocomposites at scan rate of 30mV s-1 respectively.

  12. Diketopyrrolopyrrole-Based Conjugated Polymer Entailing Triethylene Glycols as Side Chains with High Thin-Film Charge Mobility without Post-Treatments

    Energy Technology Data Exchange (ETDEWEB)

    Yang, Si-Fen [Beijing National Laboratory for Molecular Sciences, CAS Key Laboratory of Organic Solids, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190 P. R. China; University of Chinese Academy of Sciences, Beijing 100049 P. R. China; Liu, Zi-Tong [Beijing National Laboratory for Molecular Sciences, CAS Key Laboratory of Organic Solids, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190 P. R. China; Cai, Zheng-Xu [Beijing National Laboratory for Molecular Sciences, CAS Key Laboratory of Organic Solids, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190 P. R. China; Dyson, Matthew J. [Department of Materials and Centre for Plastic Electronics, Imperial College London, London SW72AZ UK; Stingelin, Natalie [Department of Materials and Centre for Plastic Electronics, Imperial College London, London SW72AZ UK; Chen, Wei [Materials Science Division, Argonne National Laboratory, 9700 Cass Avenue Lemont IL 60439 USA; Institute for Molecular Engineering, The University of Chicago, 5640 South Ellis Avenue Chicago IL 60637 USA; Ju, Hua-Jun [Beijing National Laboratory for Molecular Sciences, CAS Key Laboratory of Organic Solids, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190 P. R. China; Zhang, Guan-Xin [Beijing National Laboratory for Molecular Sciences, CAS Key Laboratory of Organic Solids, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190 P. R. China; Zhang, De-Qing [Beijing National Laboratory for Molecular Sciences, CAS Key Laboratory of Organic Solids, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190 P. R. China; University of Chinese Academy of Sciences, Beijing 100049 P. R. China

    2017-04-18

    Side chain engineering of conjugated donor-acceptor polymers is a new way to manipulate their optoelectronic properties. Two new diketopyrrolopyrrole (DPP)-terthiophene-based conjugated polymers PDPP3T-1 and PDPP3T-2, with both hydrophilic triethylene glycol (TEG) and hydrophobic alkyl chains, are reported. It is demonstrated that the incorporation of TEG chains has a significant effect on the interchain packing and thin-film morphology with noticeable effect on charge transport. Polymer chains of PDPP3T-1 in which TEG chains are uniformly distributed can self-assemble spontaneously into a more ordered thin film. As a result, the thin film of PDPP3T-1 exhibits high saturated hole mobility up to 2.6 cm(2) V-1 s(-1) without any post-treatment. This is superior to those of PDPP3T with just alkyl chains and PDPP3T-2. Moreover, the respective field effect transistors made of PDPP3T-1 can be utilized for sensing ethanol vapor with high sensitivity (down to 100 ppb) and good selectivity.

  13. Stable and Efficient Organo-Metal Halide Hybrid Perovskite Solar Cells via π-Conjugated Lewis Base Polymer Induced Trap Passivation and Charge Extraction.

    Science.gov (United States)

    Qin, Ping-Li; Yang, Guang; Ren, Zhi-Wei; Cheung, Sin Hang; So, Shu Kong; Chen, Li; Hao, Jianhua; Hou, Jianhui; Li, Gang

    2018-03-01

    High-quality pinhole-free perovskite film with optimal crystalline morphology is critical for achieving high-efficiency and high-stability perovskite solar cells (PSCs). In this study, a p-type π-conjugated polymer poly[(2,6-(4,8-bis(5-(2-ethylhexyl) thiophen-2-yl)-benzo[1,2-b:4,5-b'] dithiophene))-alt-(5,5-(1',3'-di-2-thienyl-5',7'-bis(2-ethylhexyl) benzo[1',2'-c:4',5'-c'] dithiophene-4,8-dione))] (PBDB-T) is introduced into chlorobenzene to form a facile and effective template-agent during the anti-solvent process of perovskite film formation. The π-conjugated polymer PBDB-T is found to trigger a heterogeneous nucleation over the perovskite precursor film and passivate the trap states of the mixed perovskite film through the formation of Lewis adducts between lead and oxygen atom in PBDB-T. The p-type semiconducting and hydrophobic PBDB-T polymer fills in the perovskite grain boundaries to improve charge transfer for better conductivity and prevent moisture invasion into the perovskite active layers. Consequently, the PSCs with PBDB-T modified anti-solvent processing leads to a high-efficiency close to 20%, and the devices show excellent stability, retaining about 90% of the initial power conversion efficiency after 150 d storage in dry air. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. Photoinduced electron transfer for an eosin-tyrosine conjugate. Activity of the tyrosinate anion in long-range electron transfer in a protein-like polymer matrix

    Energy Technology Data Exchange (ETDEWEB)

    Jones, G. II; Feng, Z.; Oh, C. [Boston Univ., MA (United States)

    1995-03-23

    The Xanthene dye eosin Y has been modified via a thiohydantoin link to the amine terminus of the amino acid L-tyrosine. Photochemical electron transfer involving the singlet state of the dye and the attached phenol-containing residue led to a reduction in eosin fluorescence quantum yield and lifetime for aqueous solutions at elevated pH. The conjugate provided an electron transfer product of relatively long lifetime (1 {mu}s range) observed by flash photolysis of solutions at pH 12.0, conditions under which the tyrosine moiety is ionized. The effects of binding of the conjugate in the polymer poly(vinylpyrrolidone) (PVP) on the rates of electron transfer of species of different charge type were examined. 30 refs., 5 figs., 1 tab.

  15. Driving High-Performance n- and p-type Organic Transistors with Carbon Nanotube/Conjugated Polymer Composite Electrodes Patterned Directly from Solution

    KAUST Repository

    Hellstrom, Sondra L.

    2010-07-12

    We report patterned deposition of carbon nanotube/conjugated polymer composites from solution with high nanotube densities and excellent feature resolution. Such composites are suited for use as electrodes in high-performance transistors of pentacene and C60, with bottom-contact mobilities of ?0.5 and ?1 cm2 V-1 s-1, respectively. This represents a clear step towards development of inexpensive, high-performance all-organic circuits. © 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. Polythiophene films obtained by polymerization under atmospheric pressure plasma conditions

    Energy Technology Data Exchange (ETDEWEB)

    Teslaru, T.; Topala, I., E-mail: ionut.topala@uaic.ro; Dobromir, M.; Pohoata, V.; Curecheriu, L.; Dumitrascu, N.

    2016-02-01

    The present work describes the experimental arrangement used to initiate polymerization reactions of thiophene monomer based on a dielectric barrier discharge with plane – parallel geometry, working at atmospheric pressure in argon, in turn to obtain conductive polymeric films for different applications. The resulting plasma polymerized polythiophene (pPTh) film was characterized by FT-IR, UV–Vis, XPS spectroscopy, AFM and contact angle measurements. Characterization of pPTh films showed a higher hydrophobic character and roughness, as compared with films obtained by chemical methods, and the thickness is depending on polymerization duration. Also it can conclude that our samples represent oxidised state of pPTh. As a possible application, it analysed in situ the iodine absorption phenomenon in the pPTh matrix and its time evolution by UV–Vis spectroscopy. The presence of iodine 3d{sub 5/2} and 3d{sub 3/2} peaks in the pPTh sample after absorption was identified by XPS spectroscopy. The hydrophobic pPTh film is transformed in a super hydrophilic film after absorption of iodine vapors. - Highlights: • We obtained polythiophene films (pPTh) by atmospheric pressure plasma technique. • The pPTh films showed a hydrophobic character and conducting properties. • The pPTh films were used as sensor for iodine vapors in biological environment.

  17. Highly red-shifted NIR emission from a novel anthracene conjugated polymer backbone containing Pt( ii ) porphyrins

    KAUST Repository

    Freeman, D. M. E.; Minotto, A.; Duffy, Warren; Fallon, K. J.; McCulloch, Iain; Cacialli, F.; Bronstein, H.

    2015-01-01

    -monomer is not limited to exclusively highly solubilising moieties. Interestingly, the polymer shows a red-shifted elecroluminescence maximum (510 nm) when compared to its photoluminescence maximum (450 nm) which we attribute to excimer formation. The novel polymer

  18. Synthesis and organisation of poly-substituted porphyrins in thin films for the elaboration of a highly conjugated 2D polymer

    International Nuclear Information System (INIS)

    Da Cruz, Fernande

    1997-01-01

    This research thesis addresses the production and characterization of organic thin layers for the elaboration of a wholly conjugated bi-dimensional polymer. The author first reports the synthesis of molecules belonging to the substituted porphyrin family substituted by reactive functions (acetylenic and thiophene functions). He reports how these molecules are organised under the form of a plane paving by using the Langmuir-Blodgett (LB) technique and self-assembly. It has been possible to obtain steady and organised LB films from one the synthesized porphyrins. A new method of organisation based on self-assembly has been developed, and allowed polymerizable organised porphyrin single layers to be obtained. This opens a promising way to the production of the bi-dimensional polymer. Thin films have been characterized by UV-visible spectrophotometry, IR spectrometry, X-ray diffraction, and linear dichroism [fr

  19. Interfacial molecular order of conjugated polymer in P3HT:ZnO bilayer photovoltaics and its impact on device performance

    KAUST Repository

    Wood, Sebastian

    2013-01-01

    Hybrid (organic-oxide) photovoltaic device performance is highly dependent on the nature and quality of the organic-oxide interface. This work investigates the details of interfacial morphology in terms of the molecular order of poly(3-hexylthiophene) (P3HT) at the planar interface with zinc oxide (ZnO) formed by pulsed laser deposition. Resonant Raman spectroscopy is employed as a powerful morphological probe for conjugated polymers to reveal that the interfacial P3HT is disrupted during the deposition process whereas the bulk polymer shows an increase in molecular order. External quantum efficiency measurements of P3HT:ZnO bilayer devices show that this disordered P3HT region is active in photocurrent generation. © 2013 AIP Publishing LLC.

  20. Comparison of the Photovoltaic Characteristics and Nanostructure of Fullerenes Blended with Conjugated Polymers with Siloxane-Terminated and Branched Aliphatic Side Chains

    KAUST Repository

    Kim, Do Hwan

    2013-02-12

    All-organic bulk heterojunction solar cells based on blends of conjugated polymers with fullerenes have recently surpassed the 8% efficiency mark and are well on their way to the industrially relevant ∼15% threshold. Using a low band-gap conjugated polymer, we have recently shown that polymer side chain engineering can lead to dramatic improvement in the in-plane charge carrier mobility. In this article, we investigate the effectiveness of siloxy side chain derivatization in controlling the photovoltaic performance of polymer:[6,6]-phenyl-C[71]-butyric acid methyl ester (PC71BM) blends and hence its influence on charge transport in the out-of-plane direction relevant for organic solar cells. We find that, in neat blends, the photocurrent of the polymer with siloxy side chains (PII2T-Si) is 4 times greater than that in blends using the polymer with branched aliphatic side chains (PII2T-ref). This difference is due to a larger out-of-plane hole mobility for PII2T-Si brought about by a largely face-on crystallite orientation as well as more optimal nanoscale polymer:PC71BM mixing. However, upon incorporating a common processing additive, 1,8-diiodooctane (DIO), into the spin-casting blend solution and following optimization, the PII2T-ref:PC71BM OPV device performance undergoes a large improvement and becomes the better-performing device, almost independent of DIO concentration (>1%). We find that the precise amount of DIO plays a larger role in determining the efficiency of PII2T-Si:PC71BM, and even at its maximum, the device performance lags behind optimized PII2T-ref:PC71BM blends. Using a combination of atomic force microscopy and small- and wide-angle X-ray scattering, we are able to elucidate the morphological modifications associated with the DIO-induced changes in both the nanoscale morphology and the molecular packing in blend films. © 2012 American Chemical Society.

  1. Colloidal systems of silver nanoparticles and high-regioregular cationic polythiophene with ionic-liquid-like pendant groups: Optical properties and SERS.

    Science.gov (United States)

    Kazim, Samrana; Pfleger, Jiří; Procházka, Marek; Bondarev, Dmitrij; Vohlídal, Jiří

    2011-02-15

    We report tuning of structure dependent optical properties of colloidal systems of borate-stabilized silver nanoparticles (Ag NPs) and polythiophene-based cationic polyelectrolyte with ionic-liquid like side groups: poly{3-[6-(1-methylimidazolium-3-yl)hexyl]thiophene-2,5-diyl bromide} (PMHT-Br) towards obtaining local electromagnetic field enhancement effects. Surface-enhanced Raman scattering (SERS) studies showed that the strong electromagnetic field enhancement is related to the formation of aggregates of Ag NPs achieved at the components ratio providing the charge balance between Ag NPs and cationic polythiophene, at which Ag NPs are nearly single-polymer-layer coated, their zeta potential is close to zero and they easily form aggregates in which the mean inter-particle distance enables the occurrence of desired plasmonic effects. Fluorescence quenching is efficient only in the systems with low concentrations of PMHT-Br, in which almost all polymer chains directly interact with the Ag NPs surface. Copyright © 2010 Elsevier Inc. All rights reserved.

  2. Fluorescent molecularly imprinted polymer thin films for specific protein detection prepared with dansyl ethylenediamine-conjugated O-acryloyl L-hydroxyproline.

    Science.gov (United States)

    Inoue, Yuki; Kuwahara, Atsushi; Ohmori, Kohei; Sunayama, Hirobumi; Ooya, Tooru; Takeuchi, Toshifumi

    2013-10-15

    Protein-imprinted polymers, capable of specific transduction of protein binding events into fluorescent signal change, were designed and synthesized by using dansyl ethylenediamine-conjugated O-acryloyl L-hydroxyproline (Hyp-En-Dans). Human serum albumin (HSA) was used as a model target protein and HSA-imprinted polymers (HSA-IP) were prepared on glass substrates. Specific fluorescence change was observed for HSA binding on the imprinted polymer thin film, whereas a weaker response was observed for other proteins, including bovine serum albumin, chymotrypsin, lysozyme, and avidin. The binding specificity was found to derive from the rigid structure of the hydrogen-bondable pyrrolidine moiety. Compared with SPR measurements, the non-specific binding caused by the polymer matrix and/or randomly located fluorescent monomer residues that did not compose specific binding sites did not contribute to the observed fluorescence change. These results revealed that the proposed protein-imprinting technique using Hyp-En-Dans could provide a highly selective protein-sensing platform, in which only specific binding events would be detected by fluorescent measurements. Copyright © 2013 Elsevier B.V. All rights reserved.

  3. Photophysics of conjugated polymers: interplay between Förster energy migration and defect concentration in shaping a photochemical funnel in PPV.

    Science.gov (United States)

    Saini, Sangeeta; Bagchi, Biman

    2010-07-21

    Recent single molecule experiments have suggested the existence of a photochemical funnel in the photophysics of conjugated polymers, like poly[2-methoxy-5-(2'-ethylhexyl)oxy-1,4-phenylenevinylene] (MEH-PPV). The funnel is believed to be a consequence of the presence of conformational or chemical defects along the polymer chain and efficient non-radiative energy transfer among different chromophore segments. Here we address the effect of the excitation energy dynamics on the photophysics of PPV. The PPV chain is modeled as a polymer with the length distribution of chromophores given either by a Gaussian or by a Poisson distribution. We observe that the Poisson distribution of the segment lengths explains the photophysics of PPV better than the Gaussian distribution. A recently proposed version of an extended 'particle-in-a-box' model is used to calculate the exciton energies and the transition dipole moments of the chromophores, and a master equation to describe the excitation energy transfer among different chromophores. The rate of energy transfer is assumed to be given here, as a first approximation, by the well-known Förster expression. The observed excitation population dynamics confirms the photochemical funneling of excitation energy from shorter to longer chromophores of the polymer chain. The time scale of spectral shift and energy transfer for our model polymer, with realistic values of optical parameters, is in the range of 200-300 ps. We find that the excitation energy may not always migrate towards the longest chromophore segments in the polymer chain as the efficiency of energy transfer between chromophores depends on the separation distance between the two and their relative orientation.

  4. Conjugated polymer with carboxylate groups-Hg2 + system as a turn-on fluorescence probe for label-free detection of cysteine-containing compounds

    Science.gov (United States)

    Mi, Hongyu; Guan, Mingming; Liu, Jilin; Shan, Hongyan; Fei, Qiang; Huan, Yanfu; Feng, Guodong

    2017-04-01

    In this work, a turn on fluorescent sensor, based on Hg2 + coordination conjugated polymer, was developed to detect cysteine-containing compounds. The fluorescence of conjugated polymer (poly(2,5-bis (sodium 4-oxybutyrate) -1,4 - phenylethynylene-alt-1,4-phenyleneethynylene; PPE-OBS) would be quenched by Hg2 + because of the coordination-induced aggregation and electron transfers of PPE-OBS toward Hg2 +. When there were some cysteine-containing compounds in PPE-OBS-Hg2 + system, the fluorescence of PPE-OBS would be recovered. It indicated that the PPE-OBS-Hg2 + system could be used to detect cysteine-containing compounds. Under the optimized conditions, the experiment results showed that there were particularly linear range, high sensitivity and selectivity over other amino acids. The limit of detection (LOD) of cysteine (Cys), homocysteine (Hcy) and glutathione (GSH) were 0.725 μmol L- 1, 0.982 μmol L- 1 and 1.21 μmol L- 1 by using this sensor. In addition, Cys standard recovery in several green tea drink and honey samples was also demonstrated. The recovery of Cys was range from 96.3 to 105.0% and RSD was less than 3.25%. The satisfactory results demonstrated that the proposed method could be as a potential fluorescent method for determining cysteine-containing compounds in real samples.

  5. A salt water battery with high stability and charging rates made from solution processed conjugated polymers with polar side chains

    OpenAIRE

    Moia, Davide; Giovannitti, Alexander; Szumska, Anna A.; Schnurr, Martin; Rezasoltani, Elham; Maria, Iuliana P.; Barnes, Piers R. F.; McCulloch, Iain; Nelson, Jenny

    2017-01-01

    We report a neutral salt water based battery which uses p-type and n-type solution processed polymer films as the cathode and the anode of the cell. The specific capacity of the electrodes (approximately 30 mAh cm-3) is achieved via formation of bipolarons in both the p-type and n-type polymers. By engineering ethylene glycol and zwitterion based side chains attached to the polymer backbone we facilitate rapid ion transport through the non-porous polymer films. This, combined with efficient t...

  6. Pronounced Side Chain Effects in Triple Bond-Conjugated Polymers Containing Naphthalene Diimides for n-Channel Organic Field-Effect Transistors

    KAUST Repository

    Nam, Sungho

    2018-03-23

    Three triple bond-conjugated naphthalene diimide (NDI) copolymers, poly{[N,N′-bis(2-R1)-naphthalene-1,4,5,8-bis(dicarboximide)-2,6-diyl]-alt-[(2,5-bis(2-R2)-1,4-phenylene)bis(ethyn-2,1-diyl)]} (PNDIR1-R2), were synthesized via Sonogashira coupling polymerization with varying alkyl side chains at the nitrogen atoms of the imide ring and 2,5-positions of the 1,4-diethynylbenzene moiety. Considering their identical polymer backbone structures, the side chains were found to have a strong influence on the surface morphology/nanostructure, thus playing a critical role in charge-transporting properties of the three NDI-based copolymers. Among the polymers, the one with an octyldodecyl (OD) chain at the nitrogen atoms of imide ring and a hexadecyloxy (HO) chain at the 2,5-positions of 1,4-diethynylbenzene, P(NDIOD-HO), exhibited the highest electron mobility of 0.016 cm2 V–1 s–1, as compared to NDI-based copolymers with an ethylhexyl chain at the 2,5-positions of 1,4-diethynylbenzene. The enhanced charge mobility in the P(NDIOD-HO) layers is attributed to the well-aligned nano-fiber-like surface morphology and highly ordered packing structure with a dominant edge-on orientation, thus enabling efficient in-plane charge transport. Our results on the molecular structure–charge transport property relationship in these materials may provide an insight into novel design of n-type conjugated polymers for applications in the organic electronics of the future.

  7. Indication of critical micelle concentration of nonionic surfactants with large emission change using water-soluble conjugated polymer as molecular light switch

    Energy Technology Data Exchange (ETDEWEB)

    Sun, Lilin, E-mail: sunlilin126@126.com [Anhui Key Laboratory of Chemo-Biosensing, College of Chemistry and Materials Science, Anhui Normal University, Wuhu 241000 (China); Hao, Dan; Zhang, Ping; Qian, Zhangsheng; Shen, Weili [Anhui Key Laboratory of Chemo-Biosensing, College of Chemistry and Materials Science, Anhui Normal University, Wuhu 241000 (China); Shao, Taili [Anhui Key Laboratory of Chemo-Biosensing, College of Chemistry and Materials Science, Anhui Normal University, Wuhu 241000 (China); Department of Pharmacy, Wannan Medical College, Wuhu 241000 (China); Zhu, Changqing, E-mail: zhucq@mail.ahnu.edu.cn [Anhui Key Laboratory of Chemo-Biosensing, College of Chemistry and Materials Science, Anhui Normal University, Wuhu 241000 (China)

    2013-02-15

    A new near-infrared water-soluble conjugated polymer, i.e. poly [2,5-di (propyloxysulfonate)-1,4-phenylene-ethynylene-9,10-anthrylene] (PPEASO3) was synthesized to investigate its interaction with surfactants. It was found that PPEASO3 has only a weak fluorescence emission at about 670 nm due to its self-aggregation in water and in aqueous solution containing a low concentration of nonionic surfactants, i.e. below their critical micelle concentration (CMC). However, a dramatic fluorescence enhancement with a large emission blue-shift (>40 nm) was found once the concentration of nonionic surfactants reached the CMC (especially for Triton X-100). An orange fluorescence could be observed even with naked-eyes under UV-lamp, which gave a direct indication for the micelle forming process and provided a simple method for the CMC determination of the nonionic surfactants. The CMC values determined by this method were in good agreement with those obtained by other techniques. The dramatic emission change observed could be ascribed to the intensive hydrophobic interaction between PPEASO3 and surfactants micelle, which greatly disrupts the aggregation of the polymer and increase the fluorescence efficiency of PPEASO3. Highlights: Black-Right-Pointing-Pointer Investigated the interaction of a new water-soluble conjugated polymer with surfactants. Black-Right-Pointing-Pointer The dramatic fluorescence enhancement and emission blue-shift were observed at the CMC. Black-Right-Pointing-Pointer The obvious emission color change could be observed with naked-eyes under UV-lamp. Black-Right-Pointing-Pointer Gave a direct indication for the micelle forming process. Black-Right-Pointing-Pointer Provided a simple method for the CMC determination of the nonionic surfactants.

  8. Highly red-shifted NIR emission from a novel anthracene conjugated polymer backbone containing Pt( ii ) porphyrins

    KAUST Repository

    Freeman, D. M. E.

    2015-11-30

    © The Royal Society of Chemistry 2016. We present the synthesis of a novel diphenylanthracene (DPA) based semiconducting polymer. The polymer is solubilised by alkoxy groups attached directly to a DPA monomer, meaning the choice of co-monomer is not limited to exclusively highly solubilising moieties. Interestingly, the polymer shows a red-shifted elecroluminescence maximum (510 nm) when compared to its photoluminescence maximum (450 nm) which we attribute to excimer formation. The novel polymer was utilised as a host for a covalently-linked platinum(ii) complexed porphyrin dopant. Emission from these polymers was observed in the NIR and again showed almost a 100 nm red shift from photoluminescence to electroluminescence. This work demonstrates that utilising highly aggregating host materials is an effective tool for inducing red-shifted emission in OLEDs.

  9. Hybrid active layers from a conjugated polymer and inorganic nanoparticles for organic light emitting devices with emission colour tuned by electric field

    Energy Technology Data Exchange (ETDEWEB)

    Aleshin, Andrey N; Alexandrova, Elena L; Shcherbakov, Igor P [Ioffe Physical-Technical Institute of the Russian Academy of Sciences, 26, Polytechnicheskaya Str., St Petersburg 194021 (Russian Federation)], E-mail: aleshin@transport.ioffe.ru

    2009-05-21

    We report on the investigation of the electrical and optical properties of hybrid active layers for organic devices consisting of a conjugated polymer MEH-PPV mixed with ZnO and Si nanoparticles. The effect of an electric field on the photoluminescence (PL) from a MEH-PPV : ZnO composite film is studied. We have found that in the absence of an electric field PL emission from the MEH-PPV : ZnO composites have two main maxima in the blue-red regions. Three additional minor PL maxima attributed to the exciplex states were found at {approx}420-480 nm. Application of a voltage bias to planar electrodes significantly suppresses the blue emission. Generation of excited states in the MEH-PPV : ZnO structures implies the presence of several radiative recombination mechanisms with the formation of polymer-nanoparticle complexes including exciplex states and charge transfer between the polymer and nanoparticles that can be controlled by an electric field. This effect provides the possibility to tune by an electric field the emission colour of organic light emitting diodes by combining an efficient emission from both organic/inorganic materials involved.

  10. Hybrid active layers from a conjugated polymer and inorganic nanoparticles for organic light emitting devices with emission colour tuned by electric field

    International Nuclear Information System (INIS)

    Aleshin, Andrey N; Alexandrova, Elena L; Shcherbakov, Igor P

    2009-01-01

    We report on the investigation of the electrical and optical properties of hybrid active layers for organic devices consisting of a conjugated polymer MEH-PPV mixed with ZnO and Si nanoparticles. The effect of an electric field on the photoluminescence (PL) from a MEH-PPV : ZnO composite film is studied. We have found that in the absence of an electric field PL emission from the MEH-PPV : ZnO composites have two main maxima in the blue-red regions. Three additional minor PL maxima attributed to the exciplex states were found at ∼420-480 nm. Application of a voltage bias to planar electrodes significantly suppresses the blue emission. Generation of excited states in the MEH-PPV : ZnO structures implies the presence of several radiative recombination mechanisms with the formation of polymer-nanoparticle complexes including exciplex states and charge transfer between the polymer and nanoparticles that can be controlled by an electric field. This effect provides the possibility to tune by an electric field the emission colour of organic light emitting diodes by combining an efficient emission from both organic/inorganic materials involved.

  11. Controlling the morphology and efficiency of hybrid ZnO: Polythiophene solar cells via side chain functionalization

    NARCIS (Netherlands)

    Oosterhout, S.D.; Koster, L.J.A.; Bavel, van S.S.; Loos, J.; Stenzel, O.; Thiedmann, R.; Schmidt, V.; Campo, B.J.; Cleij, T.J.; Lutzen, L.; Vanderzande, D.J.M.; Wienk, M.M.; Janssen, R.A.J.

    2011-01-01

    The efficiency of polymer – metal oxide hybrid solar cells depends critically on the intimacy of mixing of the two semiconductors. The effect of side chain functionalization on the morphology and performance of conjugated polymer:ZnO solar cells is investigated. Using an ester-functionalized side

  12. Controlling the Morphology and Efficiency of Hybrid ZnO : Polythiophene Solar Cells Via Side Chain Functionalization

    NARCIS (Netherlands)

    Oosterhout, Stefan D.; Koster, L. Jan Anton; van Bavel, Svetlana S.; Loos, Joachim; Stenzel, Ole; Thiedmann, Ralf; Schmidt, Volker; Campo, Bert; Cleij, Thomas J.; Lutzen, Laurence; Vanderzande, Dirk; Wienk, Martijn M.; Janssen, Rene A. J.

    2011-01-01

    The efficiency of polymer - metal oxide hybrid solar cells depends critically on the intimacy of mixing of the two semiconductors. The effect of side chain functionalization on the morphology and performance of conjugated polymer:ZnO solar cells is investigated. Using an ester-functionalized side

  13. Bright conjugated polymer nanoparticles containing a biodegradable shell produced at high yields and with tuneable optical properties by a scalable microfluidic device.

    Science.gov (United States)

    Abelha, T F; Phillips, T W; Bannock, J H; Nightingale, A M; Dreiss, C A; Kemal, E; Urbano, L; deMello, J C; Green, M; Dailey, L A

    2017-02-02

    This study compares the performance of a microfluidic technique and a conventional bulk method to manufacture conjugated polymer nanoparticles (CPNs) embedded within a biodegradable poly(ethylene glycol) methyl ether-block-poly(lactide-co-glycolide) (PEG 5K -PLGA 55K ) matrix. The influence of PEG 5K -PLGA 55K and conjugated polymers cyano-substituted poly(p-phenylene vinylene) (CN-PPV) and poly(9,9-dioctylfluorene-2,1,3-benzothiadiazole) (F8BT) on the physicochemical properties of the CPNs was also evaluated. Both techniques enabled CPN production with high end product yields (∼70-95%). However, while the bulk technique (solvent displacement) under optimal conditions generated small nanoparticles (∼70-100 nm) with similar optical properties (quantum yields ∼35%), the microfluidic approach produced larger CPNs (140-260 nm) with significantly superior quantum yields (49-55%) and tailored emission spectra. CPNs containing CN-PPV showed smaller size distributions and tuneable emission spectra compared to F8BT systems prepared under the same conditions. The presence of PEG 5K -PLGA 55K did not affect the size or optical properties of the CPNs and provided a neutral net electric charge as is often required for biomedical applications. The microfluidics flow-based device was successfully used for the continuous preparation of CPNs over a 24 hour period. On the basis of the results presented here, it can be concluded that the microfluidic device used in this study can be used to optimize the production of bright CPNs with tailored properties with good reproducibility.

  14. Organic Diode Rectifiers Based on a High-Performance Conjugated Polymer for a Near-Field Energy-Harvesting Circuit.

    Science.gov (United States)

    Higgins, Stuart G; Agostinelli, Tiziano; Markham, Steve; Whiteman, Robert; Sirringhaus, Henning

    2017-12-01

    Organic diodes manufactured on a plastic substrate capable of rectifying a high-frequency radio-frequency identification signal (13.56 MHz), with sufficient power to operate an interactive smart tag, are reported. A high-performance conjugated semiconductor (an indacenodithiophene-benzothiadiazole copolymer) is combined with a carefully optimized architecture to satisfy the electrical requirements for an organic-semiconductor-based logic chip. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. Control of polythiophene film microstructure and charge carrier dynamics through crystallization temperature

    KAUST Repository

    Marsh, Hilary S.; Reid, Obadiah G.; Barnes, George; Heeney, Martin; Stingelin, Natalie; Rumbles, Garry

    2014-01-01

    The microstructure of neat conjugated polymers is crucial in determining the ultimate morphology and photovoltaic performance of polymer/fullerene blends, yet until recently, little work has focused on controlling the former. Here, we demonstrate that both the long-range order along the (100)-direction and the lamellar crystal thickness along the (001)-direction in neat poly(3-hexylthiophene) (P3HT) and poly[(3,3″-didecyl[2,2′:5′, 2″-terthiophene]-5,5″-diyl)] (PTTT-10) thin films can be manipulated by varying crystallization temperature. Changes in crystalline domain size impact the yield and dynamics of photogenerated charge carriers. Time-resolved microwave conductivity measurements show that neat polymer films composed of larger crystalline domains have longer photoconductance lifetimes and charge carrier yield decreases with increasing crystallite size for P3HT. Our results suggest that the classical polymer science description of temperature-dependent crystallization of polymers from solution can be used to understand thin-film formation in neat conjugated polymers, and hence, should be considered when discussing the structural evolution of organic bulk heterojunctions. © 2014 Wiley Periodicals, Inc.

  16. Control of polythiophene film microstructure and charge carrier dynamics through crystallization temperature

    KAUST Repository

    Marsh, Hilary S.

    2014-03-22

    The microstructure of neat conjugated polymers is crucial in determining the ultimate morphology and photovoltaic performance of polymer/fullerene blends, yet until recently, little work has focused on controlling the former. Here, we demonstrate that both the long-range order along the (100)-direction and the lamellar crystal thickness along the (001)-direction in neat poly(3-hexylthiophene) (P3HT) and poly[(3,3″-didecyl[2,2′:5′, 2″-terthiophene]-5,5″-diyl)] (PTTT-10) thin films can be manipulated by varying crystallization temperature. Changes in crystalline domain size impact the yield and dynamics of photogenerated charge carriers. Time-resolved microwave conductivity measurements show that neat polymer films composed of larger crystalline domains have longer photoconductance lifetimes and charge carrier yield decreases with increasing crystallite size for P3HT. Our results suggest that the classical polymer science description of temperature-dependent crystallization of polymers from solution can be used to understand thin-film formation in neat conjugated polymers, and hence, should be considered when discussing the structural evolution of organic bulk heterojunctions. © 2014 Wiley Periodicals, Inc.

  17. Dual Functional Nanocarrier for Cellular Imaging and Drug Delivery in Cancer Cells Based on π-Conjugated Core and Biodegradable Polymer Arms.

    Science.gov (United States)

    Kulkarni, Bhagyashree; Surnar, Bapurao; Jayakannan, Manickam

    2016-03-14

    Multipurpose polymer nanoscaffolds for cellular imaging and delivery of anticancer drug are urgently required for the cancer therapy. The present investigation reports a new polymer drug delivery concept based on biodegradable polycaprolactone (PCL) and highly luminescent π-conjugated fluorophore as dual functional nanocarrier for cellular imaging and delivery vehicles for anticancer drug to cancer cells. To accomplish this goal, a new substituted caprolactone monomer was designed, and it was subjected to ring opening polymerization using a blue luminescent bishydroxyloligo-phenylenevinylene (OPV) fluorophore as an initiator. A series of A-B-A triblock copolymer building blocks with a fixed OPV π-core and variable chain biodegradable PCL arm length were tailor-made. These triblocks self-assembled in organic solvents to produce well-defined helical nanofibers, whereas in water they produced spherical nanoparticles (size ∼150 nm) with blue luminescence. The hydrophobic pocket of the polymer nanoparticle was found to be an efficient host for loading water insoluble anticancer drug such as doxorubicin (DOX). The photophysical studies revealed that there was no cross-talking between the OPV and DOX chromophores, and their optical purity was retained in the nanoparticle assembly for cellular imaging. In vitro studies revealed that the biodegradable PCL arm was susceptible to enzymatic cleavage at the intracellular lysosomal esterase under physiological conditions to release the loaded drugs. The nascent nanoparticles were found to be nontoxic to cancer cells, whereas the DOX-loaded nanoparticles accomplished more than 80% killing in HeLa cells. Confocal microscopic analysis confirmed the cell penetrating ability of the blue luminescent polymer nanoparticles and their accumulation preferably in the cytoplasm. The DOX loaded red luminescent polymer nanoparticles were also taken up by the cells, and the drug was found to be accumulated at the perinuclear environment

  18. Potentiometric and Conductometric Study of Aqueous Solutions of Lithium and Sodium Salts of Poly(thiophen-3-ylacetic acid).

    Science.gov (United States)

    Hostnik, Gregor; Vlachy, Vojko; Bondarev, Dmitrij; Jiří, Vohlídal; Cerar, Janez

    2012-09-01

    The title polymer, PTAA, practically free of ester groups was obtained by oxidative polymerization of methyl thiophen-3-ylacetate and subsequent basic hydrolysis of primary polymer. Poly(thiophen-3-ylacetic acid) has been thoroughly characterized by NMR, IR, Raman, and UV/Vis spectroscopy. The polyacid behavior during neutralization titrations with lithium and sodium hydroxides, carried out under nitrogen atmosphere, has been studied by conductometry and potentiometry. Henderson-Hasselbach plots of potentiometric titration curves show a break point at pH around 6, where the curve slope drops from 1.8 (at lower pH) to a value from 1.05 to 1.3 (at higher pH values). The UV/Vis spectra monitored during back titration show: (i) monotonous decrease of both λmax and εmax as pH decreases, (ii) the presence of the isosbestic point at 401 nm that can be ascribed to conformational transition of PTAA chains, and (iii) absence of the isosbestic point at 392 nm reported previously by other authors.

  19. Aesthetically Pleasing Conjugated Polymer: Fullerene Blends for Blue-Green Solar Cells Via Roll-to-Roll Processing

    DEFF Research Database (Denmark)

    Amb, Chad M.; Craig, Michael R.; Koldemir, Unsal

    2012-01-01

    as a thin-film deposition technique due its convenience. We report on the significant differences between the spin-coating of laboratory solar cells and slot-die coating of a blue-green colored, low bandgap polymer (PGREEN). This is one of the first demonstrations of slot-die-coated polymer solar cells OPVs......The practical application of organic photovoltaic (OPV) cells requires high throughput printing techniques in order to attain cells with an area large enough to provide useful amounts of power. However, in the laboratory screening of new materials for OPVs, spin-coating is used almost exclusively...... not utilizing poly(3-hexylthiophene):(6,6)-phenyl-C61-butyric acid methyl ester (PCBM) blends as a light absorbing layer. Through synthetic optimization, we show that strict protocols are necessary to yield polymers which achieve consistent photovoltaic behavior. We fabricated spin-coated laboratory scale OPV...

  20. Poly-Cross-Linked PEI Through Aromatically Conjugated Imine Linkages as a New Class of pH-Responsive Nucleic Acids Packing Cationic Polymers

    Science.gov (United States)

    Chen, Shun; Jin, Tuo

    2016-01-01

    Cationic polyimines polymerized through aromatically conjugated bis-imine linkages and intra-molecular cross-linking were found to be a new class of effective transfection materials for their flexibility in structural optimization, responsiveness to intracellular environment, the ability to facilitate endosome escape and cytosol release of the nucleic acids, as well as self-metabolism. When three phthalaldehydes of different substitution positions were used to polymerize highly branched low-molecular weight polyethylenimine (PEI 1.8K), the product through ortho-phthalimines (named PPOP) showed significantly higher transfection activity than its two tere- and iso-analogs (named PPTP and PPIP). Physicochemical characterization confirmed the similarity of three polyimines in pH-responded degradability, buffer capacity, as well as the size and Zeta potential of the polyplexes formed from the polymers. A mechanistic speculation may be that the ortho-positioned bis-imine linkage of PPOP may only lead to the straight trans-configuration due to steric hindrance, resulting in larger loops of intra-polymer cross-linking and more flexible backbone. PMID:26869931

  1. Synthesis, characterization and nano-structuration of poly-thiophene derivatives for organic photovoltaic solar cells; Synthese, caracterisation et nanostructuration de derives du polythiophene pour des applications en cellules photovoltaiques organiques

    Energy Technology Data Exchange (ETDEWEB)

    Berson, S

    2007-10-15

    This work is devoted to the synthesis of poly-thiophene derivatives with low bandgap and preserving high oxidation potential. Disubstituted thiophenes and 'Donor-Acceptor' bi-thiophenes were synthesized and then polymerized. The side chains of these polymers, donor or acceptor, were modified in order to tune the properties of material as well from the optical point of view as electrochemical. These polymers were also tested in blend with PCBM in bulk-heterojunction photovoltaic cells. Voc delivered by the devices showed a linear dependence according to the potential of oxidation of the polymers. Copolymers containing cyano-thiophene and alkyl- or alkoxy-thiophene showed values of 0.8 V. However, in spite of power conversion efficiency of 1 %, these performances remain lower than the one obtained with the P3HT. Optimizations in terms of morphology are certainly necessary. Indeed, the morphology of the active layer plays a key role in obtaining high power conversion efficiency. An original technique of nano-structuration of the polymer on a nano-metric scale was developed during this work, leading to the development of fibrillar P3HT. These nano-structures, presenting an important degree of order, are formed spontaneously in solution. Their rate compared to amorphous material is perfectly controllable and adjustable in solution and in solid state. Measurements of mobilities show a strong improvement of the transport of load within these fibrillar layers compared to a traditional film of P3HT obtained without annealing. Power conversion efficiencies of 3.6% on glass and 3.3 % on plastic were reached without annealing. (author)

  2. New Redox Stable Low Band Gap Conjugated Polymer Based on an EDOT-BODIPY-EDOT Repeat Unit

    Czech Academy of Sciences Publication Activity Database

    Forgie, J. C.; Skabara, P. J.; Stibor, Ivan; Vilela, F.; Vobecká, Z.

    2009-01-01

    Roč. 21, č. 9 (2009), s. 1784-1786 ISSN 0897-4756 Institutional research plan: CEZ:AV0Z40550506 Keywords : bodipy * conducting polymers * molecular electronics Subject RIV: CC - Organic Chemistry Impact factor: 5.368, year: 2009

  3. Rational design for enhancing inflammation-responsive in vivo chemiluminescence via nanophotonic energy relay to near-infrared AIE-active conjugated polymer.

    Science.gov (United States)

    Seo, Young Hun; Singh, Ajay; Cho, Hong-Jun; Kim, Youngsun; Heo, Jeongyun; Lim, Chang-Keun; Park, Soo Young; Jang, Woo-Dong; Kim, Sehoon

    2016-04-01

    H2O2-specific peroxalate chemiluminescence is recognized as a potential signal for sensitive in vivo imaging of inflammation but the effect of underlying peroxalate-emitter energetics on its efficiency has rarely been understood. Here we report a simple nanophotonic way of boosting near-infrared chemiluminescence with no need of complicated structural design and synthesis of an energetically favored emitter. The signal enhancement was attained from the construction of a nanoparticle imaging probe (∼26 nm in size) by dense nanointegration of multiple molecules possessing unique photonic features, i.e., i) a peroxalate as a chemical fuel generating electronic excitation energy in response to inflammatory H2O2, ii) a low-bandgap conjugated polymer as a bright near-infrared emitter showing aggregation-induced emission (AIE), and iii) an energy gap-bridging photonic molecule that relays the chemically generated excitation energy to the emitter for its efficient excitation. From static and kinetic spectroscopic studies, a green-emissive BODIPY dye has proven to be an efficient relay molecule to bridge the energy gap between the AIE polymer and the chemically generated excited intermediate of H2O2-reacted peroxalates. The energy-relayed nanointegration of AIE polymer and peroxalate in water showed a 50-times boosted sensing signal compared to their dissolved mixture in THF. Besides the high H2O2 detectability down to 10(-9) M, the boosted chemiluminescence presented a fairly high tissue penetration depth (>12 mm) in an ex vivo condition, which enabled deep imaging of inflammatory H2O2 in a hair-covered mouse model of peritonitis. Copyright © 2016 Elsevier Ltd. All rights reserved.

  4. Avidin-conjugated polymers with monobiotinylated antibody fragments: a new strategy for the noncovalent attachment of recombinant proteins for polymer therapeutics

    Czech Academy of Sciences Publication Activity Database

    Laga, Richard; Pola, Robert; Ulbrich, Karel; Hořejší, Magdalena; Sieglová, Irena; Král, Vlastimil; Fábry, Milan; Pechar, Michal

    2013-01-01

    Roč. 28, č. 3 (2013), s. 289-299 ISSN 0883-9115 R&D Projects: GA ČR GCP207/12/J030; GA AV ČR IAAX00500803 Institutional research plan: CEZ:AV0Z50520514 Institutional support: RVO:61389013 ; RVO:68378050 Keywords : avidin-biotin complex * polymer therapeutics * drug targeting Subject RIV: CD - Macromolecular Chemistry Impact factor: 2.500, year: 2013

  5. Hybrid thin-film solar cells comprising mesoporous titanium dioxide and conjugated polymers; Hybride Duennschicht-Solarzellen aus mesoporoesem Titandioxid und konjugierten Polymeren

    Energy Technology Data Exchange (ETDEWEB)

    Schattauer, Sylvia

    2010-12-01

    The main objective of this thesis is to study the active components and their interactions in so called organic hybrid solar cells. These consist of a thin inorganic titanium dioxide layer, combined with a polymer layer. In general, the efficiency of these hybrid solar cells is determined by the light absorption in the donor polymer, the dissociation of excitons at the heterojunction between TiO{sub 2} and polymer, as well as the generation and extraction of free charge carriers. To optimize the solar cells, the physical interactions between the materials are modified and the influences of various preparation parameters are systematically investigated. Among others, important findings regarding the optimal use of materials and preparation conditions as well as detailed investigations of fundamental factors such as film morphology and polymer infiltration are presented in more detail. First, a variety of titanium dioxide layer were produced, from which a selection for use in hybrid solar cells was made. The obtained films show differences in surface structure, film morphology and crystallinity, depending on the way how the TiO{sub 2} layer has been prepared. All these properties of the TiO{sub 2} films may strongly affect the performance of the hybrid solar cells, by influencing e.g. the exciton diffusion length, the efficiency of exciton dissociation at the hybrid interface, and the carrier transport properties. Detailed investigations were made for mesoporous TiO{sub 2} layer following a new nanoparticle synthesis route, which allows to produce crystalline particles during the synthesis. As donor component, conjugated polymers, either derivatives of cyclohexylamino-poly(p-phenylene vinylene) (PPV) or a thiophene are used. The preparation routine also includes a thermal treatment of the TiO{sub 2} layers, revealing a temperature-dependent change in morphology, but not of the crystal structure. The effects on the solar cell properties have been documented and

  6. Photomodulation spectroscopy of photocarrier dynamics, electronic defects and morphology of conducting polymers

    International Nuclear Information System (INIS)

    Vardeny, Z.V.

    1993-01-01

    A variety of techniques were used: CW photomodulation, photomodulation in femtosecond and picosecond time ranges, CW resonant Raman scattering, transient photoinduced Raman scattering, electro-absorption, degenerate four-wave mixing, spin dependent photomodulation, and absorption detected magnetic resonance. The following conducting polymers were studied: polyacetylene, polythiophene, polydiacetylene 4-BCMU, polydiethynylsilanes, polysilane embedded in a-Si:H matrix, and fullerenes

  7. Online size-exclusion high-performance liquid chromatography light scattering and differential refractometry methods to determine degree of polymer conjugation to proteins and protein-protein or protein-ligand association states.

    Science.gov (United States)

    Kendrick, B S; Kerwin, B A; Chang, B S; Philo, J S

    2001-12-15

    Characterizing the solution structure of protein-polymer conjugates and protein-ligand interactions is important in fields such as biotechnology and biochemistry. Size-exclusion high-performance liquid chromatography with online classical light scattering (LS), refractive index (RI), and UV detection offers a powerful tool in such characterization. Novel methods are presented utilizing LS, RI, and UV signals to rapidly determine the degree of conjugation and the molecular mass of the protein conjugate. Baseline resolution of the chromatographic peaks is not required; peaks need only be sufficiently separated to represent relatively pure fractions. An improved technique for determining the polypeptide-only mass of protein conjugates is also described. These techniques are applied to determining the degree of erythropoietin glycosylation, the degree of polyethylene glycol conjugation to RNase A and brain-derived neurotrophic factor, and the solution association states of these molecules. Calibration methods for the RI, UV, and LS detectors will also be addressed, as well as online methods to determine protein extinction coefficients and dn/dc values both unconjugated and conjugated protein molecules. (c)2001 Elsevier Science.

  8. Coiled coil peptides and polymer-peptide conjugates: synthesis, self-assembly, characterization and potential in drug delivery systems

    Czech Academy of Sciences Publication Activity Database

    Pechar, Michal; Pola, Robert; Laga, Richard; Braunová, Alena; Filippov, Sergey K.; Bogomolova, Anna; Bednárová, Lucie; Vaněk, O.; Ulbrich, Karel

    2014-01-01

    Roč. 15, č. 7 (2014), s. 2590-2599 ISSN 1525-7797 R&D Projects: GA ČR GCP207/12/J030 Grant - others:AV ČR(CZ) AP0802 Program:Akademická prémie - Praemium Academiae Institutional support: RVO:61389013 ; RVO:61388963 Keywords : coiled coil * self-assembly * hydrophilic polymer Subject RIV: CD - Macromolecular Chemistry; FR - Pharmacology ; Medidal Chemistry (UOCHB-X) Impact factor: 5.750, year: 2014

  9. Optimizing the conjugated side chains of quinoxaline based polymers for nonfullerene solar cells with 10.5% efficiency

    Czech Academy of Sciences Publication Activity Database

    Xu, S.; Wang, X.; Feng, L.; He, Z.; Peng, H.; Cimrová, Věra; Yuan, J.; Zhang, Z.-G.; Li, Y.; Zou, Y.

    2018-01-01

    Roč. 6, č. 7 (2018), s. 3074-3083 ISSN 2050-7488 R&D Projects: GA ČR(CZ) GA13-26542S Institutional support: RVO:61389013 Keywords : fluoroquinoxaline * polymer solar cells * high efficiency Subject RIV: BM - Solid Matter Physics ; Magnetism OBOR OECD: Condensed matter physics (including formerly solid state physics, supercond.) Impact factor: 8.867, year: 2016

  10. Dihedral angle control to improve the charge transport properties of conjugated polymers in organic field effect transistors

    Science.gov (United States)

    Dharmapurikar, Satej S.; Chithiravel, Sundaresan; Mane, Manoj V.; Deshmukh, Gunvant; Krishnamoorthy, Kothandam

    2018-03-01

    Diketopyrrolopyrrole (DPP) and i-Indigo (i-Ind) are two monomers that are widely explored as active materials in organic field effect transistor and solar cells. These two molecules showed impressive charge carrier mobility due to better packing that are facilitated by quadrupoles. We hypothesized that the copolymers of these monomers would also exhibit high charge carrier mobility. However, we envisioned that the dihedral angle at the connecting point between the monomers will play a crucial role in packing as well as charge transport. To understand the impact of dihedral angle on charge transport, we synthesized three copolymers, wherein the DPP was sandwiched between benzenes, thiophenes and furans. The copolymer of i-Indigo and furan comprising DPP showed a band gap of 1.4 eV with a very high dihedral angle of 179°. The polymer was found to pack better and the coherence length was found to be 112 Å. The hole carrier mobility of these polymer was found to be highest among the synthesized polymer i.e. 0.01 cm2/vs. The copolymer comprising benzene did not transport hole and electrons. The dihedral angle at the connecting point between i and Indigo and benzene DPP was 143 Å, which the packing and consequently charge transport properties.

  11. Preparation of dual-responsive hybrid fluorescent nano probe based on graphene oxide and boronic acid/BODIPY-conjugated polymer for cell imaging

    Energy Technology Data Exchange (ETDEWEB)

    Khoerunnisa [Department of IT Convergence, Korea National University of Transportation, Chungju 380–702 (Korea, Republic of); Kang, Eun Bi [Department of Chemical and Biological Engineering, Korea National University of Transportation, Chungju 380–702 (Korea, Republic of); Mazrad, Zihnil Adha Islamy [Department of IT Convergence, Korea National University of Transportation, Chungju 380–702 (Korea, Republic of); Lee, Gibaek [Department of Chemical and Biological Engineering, Korea National University of Transportation, Chungju 380–702 (Korea, Republic of); In, Insik [Department of IT Convergence, Korea National University of Transportation, Chungju 380–702 (Korea, Republic of); Department of Polymer Science and Engineering, Korea National University of Transportation, Chungju 380–702 (Korea, Republic of); Park, Sung Young, E-mail: parkchem@ut.ac.kr [Department of IT Convergence, Korea National University of Transportation, Chungju 380–702 (Korea, Republic of); Department of Chemical and Biological Engineering, Korea National University of Transportation, Chungju 380–702 (Korea, Republic of)

    2017-02-01

    Here, we report a pH- and thermo-responsive fluorescent nanomaterial of functionalized reduced graphene oxide (rGO) with cross-linked polymer produced via catechol-boronate diol binding mechanism. When conjugated with the hydrophobic dye boron dipyrromethane (BODIPY), this material can act as a dual-responsive nanoplatform for cells imaging. 2-Chloro-3′,4′-dihydroxyacetophenone (CCDP)-quaternized-poly(dimethylaminoethyl methacrylate-co-N-isopropylacrylamide) [C-PDN] was cross-linked with BODIPY and 4-chlorophenyl boronic acid (BA)-quaternized-poly(ethylene glycol)-g-poly(dimethylaminoethyl methacrylate-co-N-isopropylacrylamide) [BB-PPDN]. The GO was then reduced by the catechol group in the cross-linked polymer to synthesize rGO nanoparticles, which able to stabilize the quenching mechanism. This nanoplatform exhibits intense fluorescence at acidic pH and low fluorescence at physiological pH. Confocal laser scanning microscopy (CLSM) images shows bright fluorescence at lysosomal pH and total quench at physiological pH. Therefore, we have successfully developed a promising sensitive bio-imaging probe for identifying cancer cells. - Graphical abstract: [BB-PPDN]-[C-PDN]/rGO nanoparticles with boronic acid-catechol cis-diol binding mechanism toward change in pH demonstrated good biocompatibility and effective quenching for cancer cell detection. - Highlights: • Dual responsive (pH- and thermo) fluorescent nano probe was proposed for cells imaging. • The mechanism was based on cis-diol binding mechanism of boronic acid and catechol. • Reduced graphene oxide was used as quencher on nano-platform. • Detection was controlled dependent on pH based on diol compound of boron chemistry.

  12. White polymer light-emitting electrochemical cells using emission from exciplexes with long intermolecular distances formed between polyfluorene and π-conjugated amine molecules

    Science.gov (United States)

    Nishikitani, Y.; Takeuchi, H.; Nishide, H.; Uchida, S.; Yazaki, S.; Nishimura, S.

    2015-12-01

    The authors present white polymer light-emitting electrochemical cells (PLECs) fabricated with polymer blend films of poly(9,9-di-n-dodecylfluorenyl-2,7-diyl) (PFD) and π-conjugated triphenylamine molecules. The PLECs have bulk heterojunction structures composed of van der Waals interfaces between the PFD segments and the amine molecules. White-light electroluminescence (EL) can be achieved via light-mixing of the blue exciton emission from PFD and long-wavelength exciplex emission from excited complexes consisting of PFD segments (acceptors (As)) and the amine molecules (donors (Ds)). Precise control of the distances between the PFD and the amine molecules, affected through proper choice of the concentrations of PFD, amine molecules, and polymeric solid electrolytes, is critical to realizing white emission. White PLECs can be fabricated with PFD and amine molecules whose highest occupied molecular orbital (HOMO) levels range from -5.3 eV to -5.0 eV. Meanwhile, PLECs fabricated with amine molecules whose HOMO levels are lower than -5.6 eV cannot produce exciplex emission. The distances between the PFD and amine molecules of the exciplexes appear to be larger than 0.4 nm. These experimental data are explained by perturbation theory using the charge-transfer state ( A - D + ), the locally excited state ( A * D ), which is assumed to be the locally excited acceptor state in which there is no interaction with the donor molecule; and the energy gap between the HOMO levels of the PFD and the amine molecules. Color-stable white PLECs were fabricated using 4,4',4″-tris[N-(2-naphthyl)-N-phenylamino]-triphenylamine, which has a HOMO level of -5.2 eV, as the amine molecule, and the color stability of the device is a function of the fact that PFD forms exciplexes with these molecules.

  13. Self-assembled hybrid materials based on conjugated polymers and semiconductors nano-crystals for plastic solar cells

    International Nuclear Information System (INIS)

    Girolamo, J. de

    2007-11-01

    This work is devoted to the elaboration of self-assembled hybrid materials based on poly(3- hexyl-thiophene) and CdSe nano-crystals for photovoltaic applications. For that, complementary molecular recognition units were introduced as side chain groups on the polymer and at the nano-crystals' surface. Diamino-pyrimidine groups were introduced by post-functionalization of a precursor copolymer, namely poly(3-hexyl-thiophene-co-3- bromo-hexyl-thiophene) whereas thymine groups were introduced at the nano-crystals' surface by a ligand exchange reaction with 1-(6-mercapto-hexyl)thymine. However, due to their different solubility, the mixing of the two components by solution processes is difficult. A 'one-pot' procedure was developed, but this method led to insoluble aggregates without control of the hybrid composition. To overcome the solubility problem, the layer-by-layer method was used to prepare the films. This method allows a precise control of the deposition process. Experimental parameters were tested in order to evaluate their impact on the resulting film. The films morphology was investigated by microscopy and X-Ray diffraction techniques. These analyses reveal an interpenetrated structure of nano-crystals within the polymer matrix rather than a multilayered structure. Electrochemical and spectro electrochemical studies were performed on the hybrid material deposited by the LBL process. Finally the materials were tested in a solar cell configuration and the I=f(V) curves reveals a clear photovoltaic behaviour. (author)

  14. Direct observation of backbone planarization via side-chain alignment in single bulky-substituted polythiophenes

    Science.gov (United States)

    Raithel, Dominic; Simine, Lena; Pickel, Sebastian; Schötz, Konstantin; Panzer, Fabian; Baderschneider, Sebastian; Schiefer, Daniel; Lohwasser, Ruth; Köhler, Jürgen; Thelakkat, Mukundan; Sommer, Michael; Köhler, Anna; Rossky, Peter J.; Hildner, Richard

    2018-03-01

    The backbone conformation of conjugated polymers affects, to a large extent, their optical and electronic properties. The usually flexible substituents provide solubility and influence the packing behavior of conjugated polymers in films or in bad solvents. However, the role of the side chains in determining and potentially controlling the backbone conformation, and thus the optical and electronic properties on the single polymer level, is currently under debate. Here, we investigate directly the impact of the side chains by studying the bulky-substituted poly(3-(2,5-dioctylphenyl)thiophene) (PDOPT) and the common poly(3-hexylthiophene) (P3HT), both with a defined molecular weight and high regioregularity, using low-temperature single-chain photoluminescence (PL) spectroscopy and quantum-classical simulations. Surprisingly, the optical transition energy of PDOPT is significantly (˜2,000 cm‑1 or 0.25 eV) red-shifted relative to P3HT despite a higher static and dynamic disorder in the former. We ascribe this red shift to a side-chain induced backbone planarization in PDOPT, supported by temperature-dependent ensemble PL spectroscopy. Our atomistic simulations reveal that the bulkier 2,5-dioctylphenyl side chains of PDOPT adopt a clear secondary helical structural motif and thus protect conjugation, i.e., enforce backbone planarity, whereas, for P3HT, this is not the case. These different degrees of planarity in both thiophenes do not result in different conjugation lengths, which we found to be similar. It is rather the stronger electronic coupling between the repeating units in the more planar PDOPT which gives rise to the observed spectral red shift as well as to a reduced calculated electron‑hole polarization.

  15. Investigation on the Optical and Surface Morphology of Conjugated Polymer MEH-PPV:ZnO Nanocomposite Thin Films

    Directory of Open Access Journals (Sweden)

    Nurul Zayana Yahya

    2012-01-01

    Full Text Available Thin films of red color poly(2-methoxy-5(2′-ethylhexyloxy-phenylene vinylene (MEH-PPV containing different weight percent of ZnO nanoparticles were obtained by spin-coating techniques. The MEH-PPV:ZnO solutions were spin coated onto silicon and glass substrates. The spun MEH-PPV:ZnO thin films were then used to investigate optical properties by using ultraviolet-visible spectrometer (UV-Vis and photoluminescence spectrophotometer (PL. The morphologies were investigated by using field emission scanning electron microscopy (FESEM, while the identification of ZnO in the final product was determined by using energy-dispersive X-ray spectroscopy (EDS. The UV-Vis absorption band increases, while the optical bandgap decreases when the amount of ZnO nanoparticles increases. ZnO nanoparticles apparently have no effect on the conjugation segments of MEH-PPV. PL spectra show that the emission peak increases and slightly red shift as ZnO concentration increases. Based on SEM images of MEH-PPV:ZnO nanocomposite thin films, ZnO nanoparticles form agglomerated regions.

  16. Bulk heterojunction organic photovoltaic based on polythiophene-polyelectrolyte carbon nanotube composites

    Energy Technology Data Exchange (ETDEWEB)

    Reyes-Reyes, M. [Instituto de Investigacion en Comunicacion Optica, Universidad Autonoma de San Luis Potosi, Alvaro Obregon 64, San Luis Potosi (Mexico); Lopez-Sandoval, R. [Advanced Materials Department, IPICYT, Camino a la Presa San Jose 2055, Col. Lomas 4a. Seccion, San Luis Potosi 78216 (Mexico); Liu, J.; Carroll, D.L. [Center for Nanotechnology and Molecular Materials, Wake Forest University, Winston-Salem, NC (United States)

    2007-09-22

    It is shown that carbon nanotubes can be used to enhance carrier mobility for efficient removal of the charges in thin film polymer-conjugated/fullerene photovoltaic devices. The fabricated photovoltaic devices consist of poly(3-octylthiophene) (P3OT) polymer blended with undoped multiwalled carbon nanotubes (MWNTs) and carbon nanotubes doped with nitrogen (CNx-MWNTs). Nanophase formation and dispersion problems associated with the use of carbon nanotubes in polymer devices were addressed through the generation of functional groups and electrostatic attaching of the polyelectrolyte poly(dimethyldiallylamine) chloride (PDDA) in both MWNTs and CNx-MWNT systems. The resultant nanophase was highly dispersed allowing for excellent bulk heterojunction formation. Our results indicate that CNx-MWNTs enhance the efficiency of P3OT solar cells in comparison with MWNTs. (author)

  17. Highly Efficient Electrocatalysts for Oxygen Reduction Reaction Based on 1D Ternary Doped Porous Carbons Derived from Carbon Nanotube Directed Conjugated Microporous Polymers

    KAUST Repository

    He, Yafei; Gehrig, Dominik; Zhang, Fan; Lu, Chenbao; Zhang, Chao; Cai, Ming; Wang, Yuanyuan; Laquai, Fré dé ric; Zhuang, Xiaodong; Feng, Xinliang

    2016-01-01

    © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.One-dimensional (1D) porous materials have shown great potential for gas storage and separation, sensing, energy storage, and conversion. However, the controlled approach for preparation of 1D porous materials, especially porous organic materials, still remains a great challenge due to the poor dispersibility and solution processability of the porous materials. Here, carbon nanotube (CNT) templated 1D conjugated microporous polymers (CMPs) are prepared using a layer-by-layer method. As-prepared CMPs possess high specific surface areas of up to 623 m2 g-1 and exhibit strong electronic interactions between p-type CMPs and n-type CNTs. The CMPs are used as precursors to produce heteroatom-doped 1D porous carbons through direct pyrolysis. As-produced ternary heteroatom-doped (B/N/S) 1D porous carbons possess high specific surface areas of up to 750 m2 g-1, hierarchical porous structures, and excellent electrochemical-catalytic performance for oxygen reduction reaction. Both of the diffusion-limited current density (4.4 mA cm-2) and electron transfer number (n = 3.8) for three-layered 1D porous carbons are superior to those for random 1D porous carbon. These results demonstrate that layered and core-shell type 1D CMPs and related heteroatom-doped 1D porous carbons can be rationally designed and controlled prepared for high performance energy-related applications.

  18. Porous rod-like MgO complex membrane with good anti-bacterial activity directed by conjugated linolenic acid polymer

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Hua-Jie, E-mail: wanghuajie972001@163.com; Chen, Meng [Henan Normal University, College of Chemistry and Chemical Engineering (China); Mi, Li-Wei, E-mail: mlwzzu@163.com [Zhongyuan University of Technology, Center for Advanced Materials Research (China); Shi, Li-Hua [Anyang 101 Education Center (China); Cao, Ying, E-mail: caoying1130@sina.com [Zhongyuan University of Technology, Center for Advanced Materials Research (China)

    2016-02-15

    The problem of infection in the tissue engineering substitutes is driving us to seek new coating materials. We previously found that conjugated linolenic acid (CLnA) has well biocompatibility and excellent membrane-forming property. The objective of this study is to endow the anti-bacterial activity to CLnA membra ne by linking with MgO. The results showed that the CLnA polymer membrane can be loaded with porous rod-like MgO and such complex membrane showed anti-bacterial sensitivity against gram-positive bacteria (Staphylococcus aureus) even at the low concentration (0.15 μg/mm{sup 2}). In the present study, the best zone of inhibition got to 18.2 ± 0.8 mm when the amount of MgO reach 2.42 ± 0.58 μg/mm{sup 2}. It was deduced that the porous rod-like structure of MgO was directed by CLnA in its polymerization process. Such CLnA/MgO complex membrane can be helpful in the tissue engineering, medicine, food engineering, food preservation, etc. on the basis of its good anti-bacterial activity.

  19. Determination of catecholamine in human serum by a fluorescent quenching method based on a water-soluble fluorescent conjugated polymer-enzyme hybrid system.

    Science.gov (United States)

    Huang, Hui; Gao, Yuan; Shi, Fanping; Wang, Guannan; Shah, Syed Mazhar; Su, Xingguang

    2012-03-21

    In this paper, a sensitive water-soluble fluorescent conjugated polymer biosensor for catecholamine (dopamine DA, adrenaline AD and norepinephrine NE) was developed. In the presence of horse radish peroxidase (HRP) and H(2)O(2), catecholamine could be oxidized and the oxidation product of catecholamine could quench the photoluminescence (PL) intensity of poly(2,5-bis(3-sulfonatopropoxy)-1,4-phenylethynylenealt-1,4-poly(phenylene ethynylene)) (PPESO(3)). The quenching PL intensity of PPESO(3) (I(0)/I) was proportional to the concentration of DA, AD and NE in the concentration ranges of 5.0 × 10(-7) to 1.4 × 10(-4), 5.0 × 10(-6) to 5.0 × 10(-4), and 5.0 × 10(-6) to 5.0 × 10(-4) mol L(-1), respectively. The detection limit for DA, AD and NE was 1.4 × 10(-7) mol L(-1), 1.0 × 10(-6) and 1.0 × 10(-6) mol L(-1), respectively. The PPESO(3)-enzyme hybrid system based on the fluorescence quenching method was successfully applied for the determination of catecholamine in human serum samples with good accuracy and satisfactory recovery. The results were in good agreement with those provided by the HPLC-MS method.

  20. Highly Efficient Electrocatalysts for Oxygen Reduction Reaction Based on 1D Ternary Doped Porous Carbons Derived from Carbon Nanotube Directed Conjugated Microporous Polymers

    KAUST Repository

    He, Yafei

    2016-10-11

    © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.One-dimensional (1D) porous materials have shown great potential for gas storage and separation, sensing, energy storage, and conversion. However, the controlled approach for preparation of 1D porous materials, especially porous organic materials, still remains a great challenge due to the poor dispersibility and solution processability of the porous materials. Here, carbon nanotube (CNT) templated 1D conjugated microporous polymers (CMPs) are prepared using a layer-by-layer method. As-prepared CMPs possess high specific surface areas of up to 623 m2 g-1 and exhibit strong electronic interactions between p-type CMPs and n-type CNTs. The CMPs are used as precursors to produce heteroatom-doped 1D porous carbons through direct pyrolysis. As-produced ternary heteroatom-doped (B/N/S) 1D porous carbons possess high specific surface areas of up to 750 m2 g-1, hierarchical porous structures, and excellent electrochemical-catalytic performance for oxygen reduction reaction. Both of the diffusion-limited current density (4.4 mA cm-2) and electron transfer number (n = 3.8) for three-layered 1D porous carbons are superior to those for random 1D porous carbon. These results demonstrate that layered and core-shell type 1D CMPs and related heteroatom-doped 1D porous carbons can be rationally designed and controlled prepared for high performance energy-related applications.

  1. Development of melanoma-targeted polymer micelles by conjugation of a melanocortin 1 receptor (MC1R) specific ligand.

    Science.gov (United States)

    Barkey, Natalie M; Tafreshi, Narges K; Josan, Jatinder S; De Silva, Channa R; Sill, Kevin N; Hruby, Victor J; Gillies, Robert J; Morse, David L; Vagner, Josef

    2011-12-08

    The incidence of malignant melanoma is rising faster than that of any other cancer in the United States. Because of its high expression on the surface of melanomas, MC1R has been investigated as a target for selective imaging and therapeutic agents against melanoma. Eight ligands were screened against cell lines engineered to overexpress MC1R, MC4R, or MC5R. Of these, compound 1 (4-phenylbutyryl-His-dPhe-Arg-Trp-NH(2)) exhibited high (0.2 nM) binding affinity for MC1R and low (high nanomolar) affinities for MC4R and MC5R. Functionalization of the ligand at the C-terminus with an alkyne for use in Cu-catalyzed click chemistry was shown not to affect the binding affinity. Finally, formation of the targeted polymer, as well as the targeted micelle formulation, also resulted in constructs with low nanomolar binding affinity.

  2. Development and Modeling of a Novel Self-Assembly Process for Polymer and Polymeric Composite Nanoparticles

    Energy Technology Data Exchange (ETDEWEB)

    Sumpter, Bobby G. [ORNL; Carrillo, Jan-Michael Y. [ORNL; Ahn, Suk-Kyun [ORNL; Barnes, Mike D. [University of Massachusetts, Amherst; Shelton, William A. [Pacific Northwest National Laboratory (PNNL); Harrison, Robert J. [Stony Brook University (SUNY); W. Noid, Donald [Retired

    2017-10-01

    Extensive computational simulations and experiments have been used to investigate the structure, dynamics and resulting photophysical properties of a number para-phenylenevinylene (PPV) based polymers and oligomers. These studies have shown how the morphology and structure are controlled to a large extent by the nature of the solute-solvent interactions in the initial solution phase preparation. A good solvent such as dichloromethane generates non-compact structures with more of a defect-extended chain like morphology while a bad solvent such as toluene leads to compact organized and folded structures with rod-like morphologies. Secondary structural organization is induced by using the solution phase structures to generate solvent-free single molecule nanoparticles. These nanoparticles are very compact and rod shaped, consisting of near-cofacial ordering of the conjugated PPV chain backbones between folds located at tetrahedral defects (sp3 C-C bonds). The resulting photophysical properties exhibit a significant enhancement in the photoluminescence quantum yield, lifetime, and stability. In addition, the single molecule nanoparticles have Gaussian-like emission spectra with discrete center frequencies that are correlated to a conjugation length, allowing the design of nanoparticles which luminesces at a particular frequency. We followed a similar approach and applied a comparable methodology in our recent work on polythiophenes in order to study the effect of polymer architecture on nanoscale assembly. Unlike linear chains of comparable size, we observed aggregation of the bottlebrush architecture of poly(norbornene)-g-poly(3-hexylthiophene) (PNB-g-P3HT) after the freeze-drying and dissolution processes. The behavior can be attributed to a significant enhancement in the number of π-π interactions between grafted P3HT side chains.

  3. The Role of the Side Chain on the Performance of N-type Conjugated Polymers in Aqueous Electrolytes

    KAUST Repository

    Giovannitti, Alexander

    2018-04-24

    We report a design strategy that allows the preparation of solution processable n-type materials from low boiling point solvents for organic electrochemical transistors (OECTs). The polymer backbone is based on NDI-T2 copolymers where a branched alkyl side chain is gradually exchanged for a linear ethylene glycol-based side chain. A series of random copolymers was prepared with glycol side chain percentages of 0, 10, 25, 50, 75, 90, and 100 with respect to the alkyl side chains. These were characterized to study the influence of the polar side chains on interaction with aqueous electrolytes, their electrochemical redox reactions, and performance in OECTs when operated in aqueous electrolytes. We observed that glycol side chain percentages of >50% are required to achieve volumetric charging, while lower glycol chain percentages show a mixed operation with high required voltages to allow for bulk charging of the organic semiconductor. A strong dependence of the electron mobility on the fraction of glycol chains was found for copolymers based on NDI-T2, with a significant drop as alkyl side chains are replaced by glycol side chains.

  4. The Role of the Side Chain on the Performance of N-type Conjugated Polymers in Aqueous Electrolytes

    KAUST Repository

    Giovannitti, Alexander; Maria, Iuliana P.; Hanifi, David; Donahue, Mary J.; Bryant, Daniel; Barth, Katrina J.; Makdah, Beatrice E.; Savva, Achilleas; Moia, Davide; Zetek, Matyá š; Barnes, Piers R.F.; Reid, Obadiah G.; Inal, Sahika; Rumbles, Garry; Malliaras, George G.; Nelson, Jenny; Rivnay, Jonathan; McCulloch, Iain

    2018-01-01

    We report a design strategy that allows the preparation of solution processable n-type materials from low boiling point solvents for organic electrochemical transistors (OECTs). The polymer backbone is based on NDI-T2 copolymers where a branched alkyl side chain is gradually exchanged for a linear ethylene glycol-based side chain. A series of random copolymers was prepared with glycol side chain percentages of 0, 10, 25, 50, 75, 90, and 100 with respect to the alkyl side chains. These were characterized to study the influence of the polar side chains on interaction with aqueous electrolytes, their electrochemical redox reactions, and performance in OECTs when operated in aqueous electrolytes. We observed that glycol side chain percentages of >50% are required to achieve volumetric charging, while lower glycol chain percentages show a mixed operation with high required voltages to allow for bulk charging of the organic semiconductor. A strong dependence of the electron mobility on the fraction of glycol chains was found for copolymers based on NDI-T2, with a significant drop as alkyl side chains are replaced by glycol side chains.

  5. High-Voltage Polymers for High-Power Supercapacitors. Version 1

    Science.gov (United States)

    2006-05-30

    affect the supercapacitor’s performance. Subsequently, our efforts focused on fabricating polymers with high oxidation potentials to increase the power...including spin activation with out significant modifications. Electroactive polymers such as polythiophene, polyacetylene, or polyaniline can be...potentials in excess of 2 V for facile polymerization. In the present case, the triaryl ammine functionality of 2 and 3 is oxidized at the low

  6. Fluorescent strategy based on cationic conjugated polymer fluorescence resonance energy transfer for the quantification of 5-(hydroxymethyl)cytosine in genomic DNA.

    Science.gov (United States)

    Hong, Tingting; Wang, Tianlu; Guo, Pu; Xing, Xiwen; Ding, Fei; Chen, Yuqi; Wu, Jinjun; Ma, Jingwei; Wu, Fan; Zhou, Xiang

    2013-11-19

    DNA methylation is dynamically reprogrammed during early embryonic development in mammals. It can be explained partially by the discovery of 5-(hydroxymethyl)cytosine (5-hmC), 5-formylcytosine (5-fC), and 5-carboxylcytosine (5-caC), which are identified as key players involved in both active and passive demethylation pathways. As one of the ten-eleven translocation oxidation products, 5-hmC was found relatively abundant in neuron cells and embryonic stem cells. Herein we report a new method for 5-hmC quantification in genomic DNA based on CCP-FRET (cationic conjugated polymers act as the energy donor and induce fluorescence resonance energy transfer) assay combined with KRuO4 oxidation. 5-hmC in genomic DNA can be selectively transformed into 5-fC by the oxidation of KRuO4 and then labeled with hydroxylamine-BODIPY (BODIPY = 4,4-difluoro-4-bora-3a,4a-diaza-s-indacene) fluorophore through the reaction between 5-fC and hydroxylamine-BODIPY. After the fluorescently labeled DNA was captured by CCP through electrostatic interactions, a significant FRET between CCP and hydroxylamine-BODIPY fluorophore was observed. This CCP-FRET-based assay benefits from light-harvesting, large Stokes shift, and optical signal amplification properties of the CCP. Furthermore, this CCP-FRET-based assay was quite successfully demonstrated for the 5-hmC quantification in three types of cells (mESc, HeLa, HEK 293T), providing a much more convenient choice for 5-hmC quantification in genomic DNA.

  7. SERS active systems of water-soluble polythiophene and plasmonic nanoparticles: preparation and optical properties

    Czech Academy of Sciences Publication Activity Database

    Kazim, Samrana; Pfleger, Jiří; Halašová, Klára; Procházka, M.; Bondarev, D.; Vohlídal, J.

    2011-01-01

    Roč. 55, č. 2 (2011), 23905_1-23905_6 ISSN 1286-0042. [International Symposium on Flexible Organic Electronics /3./. Ouranoupolis, 06.07.2010-09.07.2010] R&D Projects: GA AV ČR KAN100500652; GA MŠk 7E10040; GA ČR GAP208/10/0941 Institutional research plan: CEZ:AV0Z40500505 Keywords : nanocomposite * SERS * .pi.-conjugated polymer s Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 0.771, year: 2011

  8. Polythiophene-carbon nanotubes composites as energy storage materials for supercapacitor application

    International Nuclear Information System (INIS)

    Thakur, A. K.; Choudhary, R. B.; Sartale, S. D.; Desai, Mangesh

    2016-01-01

    Polythiophene incorporated carbon materials have sought huge attention due to various improved electrochemical properties including enhanced electrical conductivity. Our work includes the synthesis of polythiophene (PTP)-multi-wallcarbon nanotubes (MWCNTs) via in-situ polymerization method. The homogeneous distribution of MWCNT in PTP was confirmed by Field Emission Scanning Electron Microscope (FESEM). Examination of the specimen using X-Ray diffraction (XRD), Fourier Transform-Infrared (FTIR) and Raman spectroscopy confirmed the composite formation. Other electrochemical characterizations like electrochemical impendence spectroscopy (EIS) and cyclic voltammetry (CV)of the PTP-MWCNT composite affirmed that incorporation of MWCNT improves the electrochemical properties of neat PTP including a significant increase in the capacitance. Hence making PTP-MWCNT isa better material for supercapacitor application than neat PTP.

  9. Polythiophene-carbon nanotubes composites as energy storage materials for supercapacitor application

    Energy Technology Data Exchange (ETDEWEB)

    Thakur, A. K., E-mail: anukulphyism@gmail.com; Choudhary, R. B. [CPESM-DR Laboratory, Department of Applied Physics, Indian school of mines Dhanbad-826004,India (India); Sartale, S. D.; Desai, Mangesh [Thin Films and Nanomaterials LaboratoryDepartment of Physics,Savitribai Phule Pune University, Pune-411007 (India)

    2016-05-06

    Polythiophene incorporated carbon materials have sought huge attention due to various improved electrochemical properties including enhanced electrical conductivity. Our work includes the synthesis of polythiophene (PTP)-multi-wallcarbon nanotubes (MWCNTs) via in-situ polymerization method. The homogeneous distribution of MWCNT in PTP was confirmed by Field Emission Scanning Electron Microscope (FESEM). Examination of the specimen using X-Ray diffraction (XRD), Fourier Transform-Infrared (FTIR) and Raman spectroscopy confirmed the composite formation. Other electrochemical characterizations like electrochemical impendence spectroscopy (EIS) and cyclic voltammetry (CV)of the PTP-MWCNT composite affirmed that incorporation of MWCNT improves the electrochemical properties of neat PTP including a significant increase in the capacitance. Hence making PTP-MWCNT isa better material for supercapacitor application than neat PTP.

  10. Structural, photoconductivity, and dielectric studies of polythiophene-tin oxide nanocomposites

    Energy Technology Data Exchange (ETDEWEB)

    Murugavel, S., E-mail: starin85@gmail.com; Malathi, M., E-mail: mmalathi@vit.ac.in

    2016-09-15

    Highlights: • Synthesis of polythiophene-tin oxide nanocomposites confirmed by FTIR and EDAX. • SEM shows SnO{sub 2} nanoparticles embedded within polythiophene matrix. • Stability and isoelectric point suggest nanoparticle–matrix interaction. • High dielectric constant due to high Maxwell–Wagner interfacial polarization. - Abstract: Polythiophene-tinoxide (PT-SnO{sub 2}) nanocomposites were prepared by in situ chemical oxidative polymerization, in the presence of various concentrations of SnO{sub 2} nanoparticles. Samples were characterized by X-ray diffraction, Fourier-transform infrared spectroscopy, thermogravimetric analysis, X-ray photoelectron spectroscopy and Zeta potential measurements. Morphologies and elemental compositions were investigated by transmission electron microscopy, field-emission scanning electron microscopy and energy-dispersive X-ray spectroscopy. The photoconductivity of the nanocomposites was studied by field-dependent dark and photo conductivity measurements. Their dielectric properties were investigated using dielectric spectroscopy, in the frequency range of 1kHz–1 MHz. The results indicated that the SnO{sub 2} nanoparticles in the PT-SnO{sub 2} nanocomposite were responsible for its enhanced dielectric performance.

  11. Imaging small human prostate cancer xenografts after pretargeting with bispecific bombesin-antibody complexes and targeting with high specific radioactivity labeled polymer-drug conjugates

    International Nuclear Information System (INIS)

    Patil, Vishwesh; Gada, Keyur; Panwar, Rajiv; Ferris, Craig; Khaw, Ban-An; Varvarigou, Alexandra; Majewski, Stan; Weisenberger, Andrew; Tekabe, Yared

    2012-01-01

    Bom or anti-DTPA alone (0.22 ± 0.08, p = 0.001). PC-3 xenografts pretargeted with Bom-bsFCx and targeted with 99m Tc-DSPL were visualizable by 1-3 h. Exquisite tumor uptake at 24 h (6.54 ± 1.58%ID/g) was about 15 times greater than that of Bom pretargeted controls (0.44 ± 0.17, p = 0.002). Pretargeting prostate cancer with Bom-bsCx or Bom-bsFCx enabled fast delivery of high specific radioactivity 111 In- or 99m Tc-labeled polymer-drug conjugates resulting in visualization of lesions smaller than 1-2 mm in diameter within 3 h. (orig.)

  12. Research Progress on Polymer Solar Photovoltaic Technology%聚合物太阳能光伏技术研究进展

    Institute of Scientific and Technical Information of China (English)

    全威; 李贵芳; 刘金锁; 陈磊; 程胜; 秦大山

    2012-01-01

    Polymer photovoltaic cells are becoming an .extremely active research area to meet the urgent need for clean and renewable energy managements due to their advantages of simple device structure,low cost, light weight and possibility to fabricate flexible devices. The donor and acceptor materials in the devices play the crucial role for the photovoltaic performance of the PSCs. In this article, the recent progress of the conjugated polymer donor and fullerene acceptor materials is reviewed. In the introduction of conjugated donor materials, the emphasis is put in the polythiophene derivatives and narrow bandgap D-A copolymers. The film optimization and stability are also discussed. In the end, the development prospect of polymer solar cell was given from the perspective of improving cell efficiency.%聚合物太阳电池因其结构简单、成本低、重量轻和可制成柔性器件等突出优点,近年来受到广泛关注,成为发展绿色可再生能源的重要方向。聚合物太阳电池中的给体和受体光伏材料是决定器件性能的关键,本文综述了共轭聚合物给体和富勒烯受体光伏材料的最新研究进展,并在共轭聚合物给体材料中对聚噻吩衍生物以及窄带隙D-A共聚物进行了重点介绍。同时讨论了薄膜优化和器件稳定性,最后从提高电池效率的几个方面展望了聚合物太阳电池的发展方向。

  13. Study of the nature and of the properties of paramagnetic centers observed by electron spin resonance in conjugated polymers; Etude de la nature des propriete des centres paramagnetiques observes par resonance paramagnetique electronique dans les polymeres conjugues

    Energy Technology Data Exchange (ETDEWEB)

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

    1967-06-15

    Conjugated polymers contain paramagnetic centers. It is established that these centers are free radicals and a model which defines their electronic structure is proposed. The interactions between these centers are studied, notably by dynamic polarisation experiments. Finally it is shown that the centers have catalytic properties. (author) [French] Les polymeres conjugues contiennent des centres paramagnetiques. L'origine radicalaire de ces centres est etablie et un modele precisant leur structure electronique est propose. Les interactions entre ces centres sont etudiees, notamment a l'aide d'experiences de polarisation dynamique. Des proprietes catalytiques sont mises en evidence. (auteur)

  14. Study of the nature and of the properties of paramagnetic centers observed by electron spin resonance in conjugated polymers; Etude de la nature des propriete des centres paramagnetiques observes par resonance paramagnetique electronique dans les polymeres conjugues

    Energy Technology Data Exchange (ETDEWEB)

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

    1967-06-15

    Conjugated polymers contain paramagnetic centers. It is established that these centers are free radicals and a model which defines their electronic structure is proposed. The interactions between these centers are studied, notably by dynamic polarisation experiments. Finally it is shown that the centers have catalytic properties. (author) [French] Les polymeres conjugues contiennent des centres paramagnetiques. L'origine radicalaire de ces centres est etablie et un modele precisant leur structure electronique est propose. Les interactions entre ces centres sont etudiees, notamment a l'aide d'experiences de polarisation dynamique. Des proprietes catalytiques sont mises en evidence. (auteur)

  15. Exciplex dynamics in a blend of π-conjugated polymers with electron donating and accepting properties: MDMO-PPV and PCNEPV

    NARCIS (Netherlands)

    Offermans, T.; Hal, van P.A.; Meskers, S.C.J.; Koetse, M.M.; Janssen, R.A.J.

    2005-01-01

    The photophysical properties of a solution processed blend of two semiconducting polymers with electron donating and electron accepting properties, respectively, as used in polymer photovoltaic devices have been investigated. We show that in the binary mixture of

  16. Theoretical studies of optics and charge transport in organic conducting oligomers and polymers: Rational design of improved transparent and conducting polymers

    Science.gov (United States)

    Hutchison, Geoffrey Rogers

    Theoretical studies on a variety of oligo- and polyheterocycles elucidate their optical and charge transport properties, suggesting new, improved transparent conductive polymers. First-principles calculations provide accurate methodologies for predicting both optical band gaps of neutral and cationic oligomers and intrinsic charge transfer rates. Multidimensional analysis reveals important motifs in chemical tailorability of oligoheterocycle optical and charge transport properties. The results suggest new directions for design of novel materials. Using both finite oligomer and infinite polymer calculations, the optical band gaps in polyheterocycles follow a modified particle-in-a-box formalism, scaling approximately as 1/N (where N is the number of monomer units) in short chains, saturating for long chains. Calculations demonstrate that band structure changes upon heteroatom substitution, (e.g., from polythiophene to polypyrrole) derive from heteroatom electron affinity. Further investigation of chemical variability in substituted oligoheterocycles using multidimensional statistics reveals the interplay between heteroatom and substituent in correlations between structure and redox/optical properties of neutral and cationic species. A linear correlation between band gaps of neutral and cationic species upon oxidation of conjugated oligomers, shows redshifts of optical absorption for most species and blueshifts for small band gap species. Interstrand charge-transport studies focus on two contributors to hopping-style charge transfer rates: internal reorganization energy and the electronic coupling matrix element. Statistical analysis of chemical variability of reorganization energies in oligoheterocycles proves the importance of reorganization energy in determining intrinsic charge transfer rates (e.g., charge mobility in unsubstituted oligothiophenes). Computed bandwidths across several oligothiophene crystal packing motifs show similar electron and hole bandwidths

  17. Electroassembly of smart polymer structures (role of polyelectrolytes)

    Science.gov (United States)

    Wallace, Gordon G.; Adeloju, Samuel B.; Shaw, Shannon J.

    1997-02-01

    Polymers are ubiquitous in nature, owing to their use as both structural and active components in dynamic, living systems. From a synthetic point of view man has utilized the excellent structural properties of polymers (light weight/high strength) for some decades now. However, the integration of active functional polymers into engineered systems and structures is a more recent endeavour with numerous challenges still to be overcome. Conducting electroactive polymers such as polypyrroles, polythiophenes and polyanilines are a fascinating group of functional polymers. They are electronic conductors and in addition they response to chemical or electrical stimuli in a number of ways. They are truly electrofunctional polymers. This unique combination of properties has led to the use of conducting polymers for electronic components, chemical sensors and biosensors, membranes for solution or gas separations, electromechanical actuators, electro-optical devices, biomaterials capable of controlled release of drugs or stimulation of biological processes, and for corrosion protection.

  18. Development of Polythiophene/Acrylonitrile-Butadiene Rubbers for Artificial Muscle

    Science.gov (United States)

    Thipdech, Pacharavalee; Sirivat, Anuvat

    2007-03-01

    Electroactive polymers (EAPs) can respond to the applied electrical field by an extension or a retraction. In this work, we are interested in using an elastomeric blend for electroactive applications, acrylonitirle-butadiene rubber (NBR) containing a conductive polymer (Poly(3-thiopheneacetic acid, PTAA); the latter can be synthesized via oxidative polymerization. FT-IR, Thermogravimetric analysis (TGA), ^1H-NMR, UV-visible spectroscopy, and SEM are used to characterize the conductive polymer. Electrorheological properties are measured and investigated in terms of acrylonitrile content, blending ratio, doping level, and temperature. Experiments are carried out under oscillatory shear mode and with applied electric field strength varying from 0 to 2 kV/mm. Dielectric properties, conductivities are measured and correlated with the storage modulus responses. The storage modulus sensitivity, δG'G'0of the pure rubbers increases with increasing electric field strength. They attain the maximum values of about 30% and become constant at electric strength at and above 1000 V/mm.

  19. CONJUGATED BLOCK-COPOLYMERS FOR ELECTROLUMINESCENT DIODES

    NARCIS (Netherlands)

    Hilberer, A; Gill, R.E; Herrema, J.K; Malliaras, G.G; Wildeman, J.; Hadziioannou, G

    In this article we review results obtained in our laboratory on the design and study of new light-emitting polymers. We are interested in the synthesis and characterisation of block copolymers with regularly alternating conjugated and non conjugated sequences. The blocks giving rise to luminescence

  20. Influence of Side Chain Position on the Electrical Properties of Organic Solar Cells Based on Dithienylbenzothiadiazole-alt-phenylene Conjugated Polymers

    DEFF Research Database (Denmark)

    Livi, Francesco; Zawacka, Natalia Klaudia; Angmo, Dechan

    2015-01-01

    backbone for polymer solar cells. All the polymers were roll slot die coated under ambient conditions on flexible ITO-free plastic substrates to give inverted polymer solar cell devices with an upscaled active area of 1 cm2. The best characteristics were found for the polymer carrying alkoxy side chains...... showed excellent performance under constant illumination and high temperature (exhibiting stable photovoltaic properties even after 670 h under conditions similar to ISOS-L-2 lifetime protocol). This makes P7 a good candidate for further upscaling and device optimization. The photovoltaic performance...

  1. New secondary batteries utilizing electronically conductive polymer cathodes

    Science.gov (United States)

    Martin, Charles R.; White, Ralph E.

    1989-01-01

    The objectives of this project are to characterize the transport properties in electronically conductive polymers and to assess the utility of these films as cathodes in lithium/polymer secondary batteries. During this research period, progress has been made in a literature survey of the historical background, methods of preparation, the physical and chemical properties, and potential technological applications of polythiophene. Progress has also been made in the characterization of polypyrrole flat films and fibrillar films. Cyclic voltammetry and potential step chronocoulometry were used to gain information on peak currents and potentials switching reaction rates, charge capacity, and charge retention. Battery charge/discharge studies were also performed.

  2. Effects of Molecular Stresses on Energy Transfer Pathways in Opto- and Electro-Excited Conjugated Polymers for High-Efficiency Optoelectronic Devices

    Science.gov (United States)

    2014-10-20

    dichloromethane) to obtain the yellow liquid product ( 5.94 g, yield = 90%). The scheme showed t h e synthesis route of the PTEA, TEA monomer and TE in...methanol (200 mL) to precipitate the polymers. The crude polymers were filtered, further purified by the extraction in a Soxhlet extractor with refluxing

  3. Printed biotin-functionalised polythiophene films as biorecognition layers in the development of paper-based biosensors

    Energy Technology Data Exchange (ETDEWEB)

    Ihalainen, Petri, E-mail: petri.ihalainen@abo.fi [Laboratory of Physical Chemistry, Center for Functional Materials, Åbo Akademi University, Turku (Finland); Pesonen, Markus [Physics, Center for Functional Materials, Åbo Akademi University, Turku (Finland); Sund, Pernilla [Laboratory of Polymer Technology, Center for Functional Materials, Åbo Akademi University, Turku (Finland); Viitala, Tapani [Centre for Drug Research, Division of Pharmaceutical Biosciences, University of Helsinki, Helsinki (Finland); Määttänen, Anni; Sarfraz, Jawad [Laboratory of Physical Chemistry, Center for Functional Materials, Åbo Akademi University, Turku (Finland); Wilén, Carl-Erik [Laboratory of Polymer Technology, Center for Functional Materials, Åbo Akademi University, Turku (Finland); Österbacka, Ronald [Physics, Center for Functional Materials, Åbo Akademi University, Turku (Finland); Peltonen, Jouko [Laboratory of Physical Chemistry, Center for Functional Materials, Åbo Akademi University, Turku (Finland)

    2016-02-28

    Highlights: • Inkjet-printed polythiophene films show good adhesion on ultrathin gold films. • Biotin-functionalisation of polythiophene enables specificity towards streptavidin. • Supramolecular biorecognition architectures can be prepared by printing. • The addition of each printed layer can be followed by a change in capacitance. - Abstract: The integration of flexible electronic sensors in clinical diagnostics is visioned to significantly reduce the cost of many diagnostic tests and ultimately make healthcare more accessible. This study concentrates on the characterisation of inkjet-printed bio-functionalised polythiophene films on paper-based ultrathin gold film (UTGF) electrodes and their possible application as biorecognition layers. Physicochemical surface properties (topography, chemistry, and wetting) and electrochemical characteristics of water-soluble regioirregular tetraethylene-glycol polythiophene (TEGPT) and biotin-functionalised TEGPT (b-TEGPT) films were examined and compared. In addition, their specificity towards streptavidin protein was tested. The results show that stable supramolecular biorecognition layers of insulating b-TEGPT and streptavidin were successfully fabricated on a paper-based UTGF by inkjet-printing. Good adhesion of thiophene to UTGF can be attributed to covalent linkage between sulphur and gold, whereas the stability of the streptavidin layer is due to the high affinity between biotin and streptavidin. The device introduced can be utilised in the development of biosensors for clinically relevant analytes e.g. for detecting complementary DNA oligomers or antibody–antigen complexes.

  4. α,β-Unsubstituted meso-Positioning Thienyl BODIPY: A Promising Electron Deficient Building Block for the Development of Near Infrared (NIR) p-type Donor-Acceptor (D-A) Conjugated Polymers

    KAUST Repository

    Squeo, Benedetta

    2018-02-27

    It is demonstrated that α,β-unsubstituted meso-positioning thienyl BODIPY is an electron deficient unit that leads to the development of ultra low optical band gap (Egopt < 1 eV) π-conjugated D-A quarterthiophene polymers. Furthermore, it is revealed that the optoelectronic, electrochemical and charge transporting properties of the resulting α,β-unsubstituted meso-positioning thienyl BODIPY quaterthiophene-based polymers are alkyl side chain positioning dependent. Tail-to-tail (TT) positioning of the alkyl side chains at the two central thiophenes of the quaterthiophene segment results to lower Egopt, higher energy levels and increased hole mobility as compared to head-to-head (HH) positioning. Finally, even though the synthesized polymers exhibit high electron affinity, higher even to that of the fullerene derivative [6,6]-phenyl-C71-butyric acid methyl ester (PC71BM), they present only p-type behaviour in field effect transistors (FETs) independent to the alkyl side chain positioning.

  5. Conductivity in redox modified conducting polymers. In-situ conductivity of poly(cyclopentadithiophenes) bearing p-nitrophenyl and 4-N-methylpyridinium groups

    Energy Technology Data Exchange (ETDEWEB)

    Zotti, G. [Consiglio Nazionale delle Ricerche, (Italy). Istituto di Polarografia ed Elettrochimica Preparativa; Berlin, A. [Milan Univ. (Italy). Dipartimento di Chimica Organica e Industriale; Pagani, G. [Milan Univ. (Italy). Dipartimento di Chimica Organica e Industriale; Schiavon, G. [Consiglio Nazionale delle Ricerche, (Italy). Istituto di Polarografia ed Elettrochimica Preparativa; Zecchin, S. [Consiglio Nazionale delle Ricerche, (Italy). Istituto di Polarografia ed Elettrochimica Preparativa

    1995-01-01

    Redox-modified polythiophenes exhibiting the highest mixed-valence conductivities of any polymer containing a pendant redox group are reported. The ordering of the polymer, in which the backbone has been oxidized to a bipolaron conducting state and the redox sites have been reduced to a mixed-valence conducting state, encourages inter-site hopping and results in the high conductivities. Electron interactions are shown not have an influence on the conduction. (orig.)

  6. Application of polythiophene to methanol vapor detection: an ab initio study.

    Science.gov (United States)

    Shokuhi Rad, Ali

    2015-11-01

    The interaction of methanol with terthiophene (3PT; a model of polythiophene) was investigated using density functional theory (DFT) at the BLYP-D3/6-31+G(d,p) level of theory. The computed density of states (DOS) pointed to considerable orbital hybridization upon the interaction of methanol with 3PT. Natural population analysis (NPA) was used to determine the charge distribution as well as the net charge transfer within the 3PT-methanol system, and thus to assess the sensing ability of terthiophene. The computed dipole moment revealed that the dielectric μ D changes upon the interaction of methanol with 3PT. Using calculated changes in the HOMO-LUMO energy gap, it was deduced that the electronic properties of 3PT are sensitive to the interaction of 3PT with methanol. After full energy relaxation, the interaction energy of methanol with 3PT in the most stable configuration was calculated to be -16.4 (counterpoise-corrected energy: -13.5) kJ mol(-1), providing proof that methanol is physisorbed by 3PT. Graphical Abstract Adsorption of methanol on polythiophene.

  7. A star-shaped polythiophene dendrimer coating for solid-phase microextraction of triazole agrochemicals.

    Science.gov (United States)

    Abolghasemi, Mir Mahdi; Habibiyan, Rahim; Jaymand, Mehdi; Piryaei, Marzieh

    2018-02-14

    A nanostructured star-shaped polythiophene dendrimer was prepared and used as a fiber coating for headspace solid phase microextraction of selected triazolic pesticides (tebuconazole, hexaconazole, penconazole, diniconazole, difenoconazole, triticonazole) from water samples. The dendrimer with its large surface area was characterized by thermogravimetric analysis, UV-Vis spectroscopy and field emission scanning electron microscopy. It was placed on a stainless steel wire for use in SPME. The experimental conditions for fiber coating, extraction, stirring rate, ionic strength, pH value, desorption temperature and time were optimized. Following thermal desorption, the pesticides were quantified by GC-MS. Under optimum conditions, the repeatability (RSD) for one fiber (for n = 3) ranges from 4.3 to 5.6%. The detection limits are between 8 and 12 pg mL -1 . The method is fast, inexpensive (in terms of equipment), and the fiber has high thermal stability. Graphical abstract Schematic presentation of a nanostructured star-shaped polythiophene dendrimer for use in headspace solid phase microextraction of the triazolic pesticides (tebuconazole, hexaconazole, penconazole, diniconazole, difenoconazole, triticonazole). They were then quantified by gas chromatography-mass spectrometry.

  8. Chalcogenophene comonomer comparison in small band gap diketopyrrolopyrrole-based conjugated polymers for high-performing field-effect transistors and organic solar cells

    KAUST Repository

    Ashraf, Raja Shahid

    2015-01-28

    The design, synthesis, and characterization of a series of diketopyrrolopyrrole-based copolymers with different chalcogenophene comonomers (thiophene, selenophene, and tellurophene) for use in field-effect transistors and organic photovoltaic devices are reported. The effect of the heteroatom substitution on the optical, electrochemical, and photovoltaic properties and charge carrier mobilities of these polymers is discussed. The results indicate that by increasing the size of the chalcogen atom (S < Se < Te), polymer band gaps are narrowed mainly due to LUMO energy level stabilization. In addition, the larger heteroatomic size also increases intermolecular heteroatom-heteroatom interactions facilitating the formation of polymer aggregates leading to enhanced field-effect mobilities of 1.6 cm2/(V s). Bulk heterojunction solar cells based on the chalcogenophene polymer series blended with fullerene derivatives show good photovoltaic properties, with power conversion efficiencies ranging from 7.1-8.8%. A high photoresponse in the near-infrared (NIR) region with excellent photocurrents above 20 mA cm-2 was achieved for all polymers, making these highly efficient low band gap polymers promising candidates for use in tandem solar cells. (Graph Presented).

  9. The Photo-Physics of Polythiophene Nanoparticles for Biological Applications.

    Science.gov (United States)

    Bargigia, Ilaria; Zucchetti, Elena; Srimath Kandada, Ajay Ram; Moreira, Miguel; Bossio, Caterina; Wong, Walter; Miranda, Paulo; Decuzzi, Paolo; Soci, Cesare; D'Andrea, Cosimo; Lanzani, Guglielmo

    2018-05-01

    In this work the photo-physics of poly(3-hexyltiophene) nanoparticles (NPs) is investigated in the context of their biological applications. The NPs made as colloidal suspensions in aqueous buffers present a distinct absorption band in the low energy region. Based on systematic analysis of absorption and transient absorption spectra taken under different pH conditions, this band is associated to charge transfer states generated by the polarization of loosely bound polymer chains and originated from complexes formed with electron withdrawing species. Importantly, the ground state depletion of these states upon photo-excitation is active even in the microsecond timescales, suggesting that they act as precursor states for long-living polarons which could be beneficial for cellular stimulation. Preliminary results of transient absorption microscopy of NPs internalized within the cells reveal the presence of long-living species, further substantiating their relevance in bio-interfaces. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. Carbon Nanotube Web with Carboxylated Polythiophene "Assist" for High-Performance Battery Electrodes.

    Science.gov (United States)

    Kwon, Yo Han; Park, Jung Jin; Housel, Lisa M; Minnici, Krysten; Zhang, Guoyan; Lee, Sujin R; Lee, Seung Woo; Chen, Zhongming; Noda, Suguru; Takeuchi, Esther S; Takeuchi, Kenneth J; Marschilok, Amy C; Reichmanis, Elsa

    2018-04-24

    A carbon nanotube (CNT) web electrode comprising magnetite spheres and few-walled carbon nanotubes (FWNTs) linked by the carboxylated conjugated polymer, poly[3-(potassium-4-butanoate) thiophene] (PPBT), was designed to demonstrate benefits derived from the rational consideration of electron/ion transport coupled with the surface chemistry of the electrode materials components. To maximize transport properties, the approach introduces monodispersed spherical Fe 3 O 4 (sFe 3 O 4 ) for uniform Li + diffusion and a FWNT web electrode frame that affords characteristics of long-ranged electronic pathways and porous networks. The sFe 3 O 4 particles were used as a model high-capacity energy active material, owing to their well-defined chemistry with surface hydroxyl (-OH) functionalities that provide for facile detection of molecular interactions. PPBT, having a π-conjugated backbone and alkyl side chains substituted with carboxylate moieties, interacted with the FWNT π-electron-rich and hydroxylated sFe 3 O 4 surfaces, which enabled the formation of effective electrical bridges between the respective components, contributing to efficient electron transport and electrode stability. To further induce interactions between PPBT and the metal hydroxide surface, polyethylene glycol was coated onto the sFe 3 O 4 particles, allowing for facile materials dispersion and connectivity. Additionally, the introduction of carbon particles into the web electrode minimized sFe 3 O 4 aggregation and afforded more porous FWNT networks. As a consequence, the design of composite electrodes with rigorous consideration of specific molecular interactions induced by the surface chemistries favorably influenced electrochemical kinetics and electrode resistance, which afforded high-performance electrodes for battery applications.

  11. Synthesis, characterization and the release kinetics of antiproliferative agents from polyamidoamine conjugates

    CSIR Research Space (South Africa)

    Aderibigbe, BA

    2015-01-01

    Full Text Available Polyamidoamine conjugates containing curcumin and bisphosphonate were synthesized via a one-pot aqueous phase Michael addition reaction. In the design of the conjugate, bisphosphonate formed an integral part of the polymer carrier backbone. Curcumin...

  12. Synthesis of Isothianaphthene (ITN and 3,4-Ethylenedioxy-Thiophene (EDOT-Based Low-Bandgap Liquid Crystalline Conjugated Polymers

    Directory of Open Access Journals (Sweden)

    Hiromasa Goto

    2013-05-01

    Full Text Available Copolymers, consisting of isothianaphthene and phenylene derivatives with liquid crystal groups, were synthesized via Migita-Kosugi-Stille polycondensation reaction. IR absorption, UV-vis optical absorption, and PL spectroscopy measurements were carried out. Thermotropic liquid crystallinity of the polymers with bandgap of ~2.5 eV was confirmed.

  13. Pronounced Side Chain Effects in Triple Bond-Conjugated Polymers Containing Naphthalene Diimides for n-Channel Organic Field-Effect Transistors

    KAUST Repository

    Nam, Sungho; Hahm, Suk Gyu; Khim, Dongyoon; Kim, Hwajeong; Sajoto, Tissa; Ree, Moonhor; Marder, Seth R.; Anthopoulos, Thomas D.; Bradley, Donal D.C.; Kim, Youngkyoo

    2018-01-01

    on the surface morphology/nanostructure, thus playing a critical role in charge-transporting properties of the three NDI-based copolymers. Among the polymers, the one with an octyldodecyl (OD) chain at the nitrogen atoms of imide ring and a hexadecyloxy (HO

  14. Polymers targeting habitual diseases

    Science.gov (United States)

    The use of polymeric drug conjugates mainly for the treatment for cancer therapy has been addressed, but these polymers also find their way in treatment of various lifestyle disorders like diabetes, hypertension, cardiovascular diseases etc. The focus is being laid to develop biodegradable polymer ...

  15. Low coercive field and conducting nanocomposite formed by Fe3O4 and poly(thiophene)

    International Nuclear Information System (INIS)

    Silva, R.A.; Santos, M.J.L.; Rinaldi, A.W.; Zarbin, A.J.G.; Oliveira, M.M.; Santos, I.A.; Cotica, L.F.; Coellho, A.A.; Rubira, A.F.; Girotto, E.M.

    2007-01-01

    Magnetite and poly(thiophene) composites have been produced by in situ monomer oxidation. Fourier transform infrared (FTIR) and X-ray diffraction (XRD) confirmed the presence of Fe 3 O 4 as particle agglomerates ranging from 15 to ca. 54 nm in size. Transmission electron micrographs (TEMs) revealed a face-to-face structure in both the pure magnetite and the nanocomposite. Typical superparamagnetic (ferrimagnetic) curves have been observed, whereas the relatively weak magnetic field employed in measurement, 200 Oe, was sufficient to split the curves completely. Zero field cooling (ZFC) and field cooling (FC) curves coincide only above room temperature, indicating that the characteristic blocking temperature (T B ) for superparamagnetic particles in this assembly is above room temperature. - Graphical abstract: TEM image of magnetite/poly(thiophene) nanocomposite

  16. Large thermoelectric efficiency of doped polythiophene junction: A density functional study

    Science.gov (United States)

    Golsanamlou, Zahra; Bagheri Tagani, Meysam; Rahimpour Soleimani, Hamid

    2018-06-01

    The thermoelectric properties of polythiophene (PT) coupled to the Au (111) electrodes are studied based on density functional theory with nonequilibrium Green function formalism. Specially, the effect of Li and Cl adsorbents on the thermoelectric efficiency of the PT junction is investigated in different concentrations of the dopants for two lengths of the PT. Results show that the presence of dopants can bring the structural changes in the oligomer and modify the arrangement of the molecular levels leading to the dramatic changes in the transmission spectra of the junction. Therefore, the large enhancement in thermopower and consequently figure of merit is obtained by dopants which makes the doped PT junction as a beneficial thermoelectric device.

  17. Cell Penetrating Polymers Containing Guanidinium Trigger Apoptosis in Human Hepatocellular Carcinoma Cells unless Conjugated to a Targeting N-Acetyl-Galactosamine Block.

    Science.gov (United States)

    Tan, Zhe; Dhande, Yogesh K; Reineke, Theresa M

    2017-12-20

    A series of 3-guanidinopropyl methacrylamide (GPMA)-based polymeric gene delivery vehicles were developed via aqueous reversible addition-fragmentation chain transfer (RAFT) polymerization. The polymers have been evaluated for their cellular internalization ability, transfection efficiency, and cytotoxicity. Two homopolymers: P(GPMA 20 ), P(GPMA 34 ), were synthesized to study the effect of guanidium polymer length on delivery efficiency and toxicity. In addition, an N-acetyl-d-galactosamine (GalNAc)-based hydrophilic block was incorporated to produce diblock polymers, which provides a neutral hydrophilic block that sterically protects plasmid-polymer complexes (polyplexes) from colloidal aggregation and aids polyplex targeting to hepatocytes via binding to asialoglycoprotein receptors (ASGPRs). Polyplexes formed with P(GPMA x ) (x = 20, 34) homopolymers were shown to be internalized via both energy-dependent and independent pathways, whereas polyplexes formed with block polymers were internalized through endocytosis. Notably, P(GPMA x ) polyplexes enter cells very efficiently but are also very toxic to human hepatocellular carcinoma (HepG2) cells and triggered cell apoptosis. In comparison, the presence of a carbohydrate block in the polymer structures reduced the cytotoxicity of the polyplex formulations and increased gene delivery efficiency with HepG2 cells. Transfection efficiency and toxicity studies were also carried out with HEK 293T (human embryonic kidney) cells for comparison. Results showed that polyplexes formed with the P(GPMA x ) homopolymers exhibit much higher transfection efficiency and lower toxicity with HEK 293T cells. The presence of the carbohydrate block did not further increase transfection efficiency in comparison to the homopolymers with HEK 293T cells, likely due to the lack of ASGPRs on the HEK 293T cell line. This study revealed that although guanidinium-based polymers have high membrane permeability, their application as plasmid

  18. Conducting Polymers for Neutron Detection

    International Nuclear Information System (INIS)

    Clare Kimblin; Kirk Miller; Bob Vogel; Bill Quam; Harry McHugh; Glen Anthony; Steve Jones; Mike Grover

    2007-01-01

    Conjugated polymers have emerged as an attractive technology for large-area electronic applications. As organic semiconductors, they can be used to make large-area arrays of diodes or transistors using fabrication techniques developed for polymer coatings, such as spraying and screen-printing. We have demonstrated both neutron and alpha detection using diodes made from conjugated polymers and have done preliminary work to integrate a boron carbide layer into the conventional polymer device structure to capture thermal neutrons. The polymer devices appear to be insensitive to gamma rays, due to their small physical thickness and low atomic number

  19. Diketopyrrolopyrrole polymers for organic solar cells

    NARCIS (Netherlands)

    Li, Wei Wei; Hendriks, K.H.; Wienk, M.M.; Janssen, R.A.J.

    2016-01-01

    Conspectus Conjugated polymers have been extensively studied for application in organic solar cells. In designing new polymers, particular attention has been given to tuning the absorption spectrum, molecular energy levels, crystallinity, and charge carrier mobility to enhance performance. As a

  20. Hybrid polymer-inorganic photovoltaic cells

    NARCIS (Netherlands)

    Beek, W.J.E.; Janssen, R.A.J.; Merhari, L.

    2009-01-01

    Composite materials made from organic conjugated polymers and inorganic semiconductors such as metal oxides attract considerable interest for photovoltaic applications. Hybrid polymer-inorganic solar cells offer the opportunity to combine the beneficial properties of the two materials in charge