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Sample records for water-soluble conjugated polymers

  1. Water-soluble conjugated polymers for fluorescent-enzyme assays.

    Science.gov (United States)

    Feng, Fude; Liu, Libing; Yang, Qiong; Wang, Shu

    2010-08-17

    Enzyme assays are receiving more and more research and application interest because of the rapidly increasing demands of clinical diagnosis, environmental analysis, drug discovery, and molecular biology. Water-soluble light-harvesting conjugated polymers (CPs) coordinate the action of a large number of absorbing units to afford an amplified fluorescence signal, which makes them useful as optical platforms in highly sensitive chemical and biological sensors. This Feature Article highlights recent developments of water-soluble CPs for fluorescent assays of enzymes. Different signal transduction mechanisms, such as electron transfer, fluorescence resonance energy transfer (FRET), and aggregation or conformation changes of CPs, are employed in these assays according to the dissimilar nature of enzymes. Potential challenges and future research directions in these approaches based on CPs are also discussed. Copyright © 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. Water-soluble fluorescent conjugated polymers and their interactions with biomacromolecules for sensitive biosensors.

    Science.gov (United States)

    Feng, Xuli; Liu, Libing; Wang, Shu; Zhu, Daoben

    2010-07-01

    Over the past decades, water-soluble conjugated polymers (CPs) have gained increasing attention as optical platforms for sensitive detection of biomacromolecules (DNA, protein and cell) due to the amplification of fluorescent signals. To meet the requirement for high throughput assays, chip and microarray techniques based on CPs have also been developed. Very recently, fluorescence imaging in vivo and at the cellular level have also been successfully accomplished using these water-soluble CPs. In this tutorial review, we provide a brief review of the synthesis and optical properties of CPs, focusing especially on their applications in biosensors and cell imaging.

  3. Delivery of antisense oligonucleotides using HPMA polymer: synthesis of A thiol polymer and its conjugation to water-soluble molecules.

    Science.gov (United States)

    Wang, L; Kristensen, J; Ruffner, D E

    1998-01-01

    Here, we report the synthesis and characterization of an HPMA-based polymer for use as a carrier for the delivery of water soluble drugs. The polymer contains active-sulfhydryl groups for coupling of ligands through a disulfide linkage. The polymer can also be prepared containing pendant amino groups in addition to the active-sulfhydryl moiety. This allows the use of different chemistries to conjugate a variety of ligands to the polymer. We demonstrate that a sulfhydryl-terminated antisense oligonucleotide can be efficiently and rapidly conjugated to the polymer. The polymer-oligonucleotide conjugate is efficiently taken up by cultured cells.

  4. [A water-soluble synthetic polymer, alpha,beta-poly(hydroxyalkyl)-DL-asparamide, and conjugating drug].

    Science.gov (United States)

    Zhang, Z; Tang, G; Chen, Q; Wang, B; Ma, M; Zhang, X

    1999-12-01

    A water-soluble polymer alpha,beta-poly (hydroxyalkyl)-DL-asparamide was synthesized by polysuccinimide(PSI) and different lengths of hydroxyalkyls, including alpha,beta-poly(hydroxyethyl)-DL-asparamide(PHEA), alpha,beta-poly(hydroxypropyl)-DL-asparamide(PHPA), and alpha,beta-poly(hydroxybutyl)-DL-asparamide(PHBA). These polymers were characterized by differential scanning calorimetry(DSC) and infrared spectrophotometry(IR). Stability and acutetoxicity of these polymers were studied. The experiment indicated that these materials were of low-toxicity and high stability. Acetylsalicylic acid, as a model drug, was conjugated into polymers; the drug loadings were 38.63%, 37.68% and 38.70% respectively. Polymer drugs were made into cylinder, and in-vivo release in rabbits was set out. It showed that the longer the spacer was linked into the polymer, the faster the drug was released.

  5. Design and synthesis of monofunctionalized, water-soluble conjugated polymers for biosensing and imaging applications.

    Science.gov (United States)

    Traina, Christopher A; Bakus, Ronald C; Bazan, Guillermo C

    2011-08-17

    Water-soluble conjugated polymers with controlled molecular weight characteristics, absence of ionic groups, high emission quantum yields, and end groups capable of selective reactions of wide scope are desirable for improving their performance in various applications and, in particular, fluorescent biosensor schemes. The synthesis of such a structure is described herein. 2-Bromo-7-iodofluorene with octakis(ethylene glycol) monomethyl ether chains at the 9,9'-positions, i.e., compound 4, was prepared as the reactive premonomer. A high-yielding synthesis of the organometallic initiator (dppe)Ni(Ph)Br (dppe = 1,2-bis(diphenylphosphino)ethane) was designed and implemented, and the resulting product was characterized by single-crystal X-ray diffraction techniques. Polymerization of 4 by (dppe)Ni(Ph)Br can be carried out in less than 30 s, affording excellent control over the average molecular weight and polydispersity of the product. Quenching of the polymerization with [2-(trimethylsilyl)ethynyl]magnesium bromide yields silylacetylene-terminated water-soluble poly(fluorene) with a photoluminescence quantum efficiency of 80%. Desilylation, followed by copper-catalyzed azide-alkyne cycloaddition reaction, yields a straightforward route to introduce a wide range of specific end group functionalities. Biotin was used as an example. The resulting biotinylated conjugated polymer binds to streptavidin and acts as a light-harvesting chromophore to optically amplify the emission of Alexa Fluor-488 chromophores bound onto the streptavidin. Furthermore, the biotin end group makes it possible to bind the polymer onto streptavidin-functionalized cross-linked agarose beads and thereby incorporate a large number of optically active segments.

  6. The Comparison of In Vivo Properties of Water-Soluble HPMA-Based Polymer Conjugates with Doxorubicin Prepared by Controlled RAFT or Free Radical Polymerization

    National Research Council Canada - National Science Library

    P Chytil; M Sírová; E Koziolová; K Ulbrich; B Ríhová; T Etrych

    2015-01-01

      Two conjugates of anticancer drug doxorubicin (Dox) covalently bound by the hydrolytically degradable hydrazone bond to the polymer carrier based on water-soluble N-(2-hydroxypropyl) methacrylamide (HPMA...

  7. Efficient separation of conjugated polymers using a water soluble glycoprotein matrix: from fluorescence materials to light emitting devices.

    Science.gov (United States)

    Hendler, Netta; Wildeman, Jurjen; Mentovich, Elad D; Schnitzler, Tobias; Belgorodsky, Bogdan; Prusty, Deepak K; Rimmerman, Dolev; Herrmann, Andreas; Richter, Shachar

    2014-03-01

    Optically active bio-composite blends of conjugated polymers or oligomers are fabricated by complexing them with bovine submaxilliary mucin (BSM) protein. The BSM matrix is exploited to host hydrophobic extended conjugated π-systems and to prevent undesirable aggregation and render such materials water soluble. This method allows tuning the emission color of solutions and films from the basic colors to the technologically challenging white emission. Furthermore, electrically driven light emitting biological devices are prepared and operated. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. Solvent polarity effect on chain conformation, film morphology, and optical properties of a water-soluble conjugated polymer.

    Science.gov (United States)

    Xu, Zhihua; Tsai, Hsinhan; Wang, Hsing-Lin; Cotlet, Mircea

    2010-09-16

    The solvent polarity effect on chain conformation, film morphology, and photophysical properties of a nonionic water-soluble conjugated polymer (WSCP), poly[2,5-bis(diethylaminetetraethylene glycol)phenylene vinylene] (DEATG-PPV) is investigated in detail. The combination of stationary absorption and photoluminescence (PL) spectroscopy, time-resolved PL spectroscopy, and fluorescence correlation spectroscopy methods enables us to probe the chain conformation of DEATG-PPV, down to the level of a single chain when working with extremely diluted solutions. The use of correlated atomic force microscopy and confocal fluorescence lifetime imaging microscopy measurements of drop-casted DEATG-PPV films reveals the intrinsic relationship between chain conformation, film morphology, and optical properties. Depending on solvent polarity, DEATG-PPV presents extended, coiled, and collapsed chain conformations in solutions, which lead to distinct morphology and optical properties in solid films. Our work presents a pathway to control and characterize the film morphologies of WSCPs toward the optimal performance of various optoelectronic devices.

  9. The comparison of in vivo properties of water-soluble HPMA-based polymer conjugates with doxorubicin prepared by controlled RAFT or free radical polymerization.

    Science.gov (United States)

    Chytil, P; Šírová, M; Koziolová, E; Ulbrich, K; Říhová, B; Etrych, T

    2015-01-01

    Two conjugates of anticancer drug doxorubicin (Dox) covalently bound by the hydrolytically degradable hydrazone bond to the polymer carrier based on water-soluble N-(2-hydroxypropyl) methacrylamide (HPMA) copolymers were synthesized and their properties were compared, namely their behavior in vivo. The polymer carriers differed in dispersity due to different methods of synthesis; the carrier with relatively high dispersity (HD) was prepared by free radical polymerization (Mw=29,900 g/mol, D=1.75) and the carrier with low dispersity (LD) by controlled radical polymerization (Mw=30,000 g/mol, D=1.13). Both polymer-Dox conjugates showed prolonged blood circulation and tumor accumulation of the drug in comparison with the free drug; e.g. the tumor-to-blood ratio for the polymer-bound Dox was 3-5 times higher. The LD polymer-Dox conjugate exhibited moderately higher tumor accumulation than the HD one at a dose of 1x15 mg Dox (eq.)/kg. Also, their anti-tumor activity did not differ when injected at this dose. However, the increase of the dose to 1x25 mg Dox (eq.)/kg resulted in the enhanced therapeutic activity of the conjugates, especially of the LD one with 100% of long-term survivals. The dispersity of polymer drug carriers influenced the tumor accumulation rate, which affected the overall anti-cancer activity of polymer-drug conjugates.

  10. Photophysical Diversity of Water-Soluble Fluorescent Conjugated Polymers Induced by Surfactant Stabilizers for Rapid and Highly Selective Determination of 2,4,6-Trinitrotoluene Traces.

    Science.gov (United States)

    Alizadeh, Naader; Akbarinejad, Alireza; Ghoorchian, Arash

    2016-09-21

    The increasing application of fluorescence spectroscopy in development of reliable sensing platforms has triggered a lot of research interest for the synthesis of advanced fluorescent materials. Herein, we report a simple, low-cost strategy for the synthesis of a series of water-soluble conjugated polymer nanoparticles with diverse emission range using cationic (hexadecyltrimethylammonium bromide, CTAB), anionic (sodium dodecylbenzenesulfonate, SDBS), and nonionic (TX114) surfactants as the stabilizing agents. The role of surfactant type on the photophisical and sensing properties of resultant polymers has been investigated using dynamic light scattering (DLS), FT-IR, UV-vis, fluorescence, and energy dispersive X-ray (EDS) spectroscopies. The results show that the surface polarity, size, and spectroscopic and sensing properties of conjugated polymers could be well controlled by the proper selection of the stabilizer type. The fluorescent conjugated polymers exhibited fluorescence quenching toward nitroaromatic compounds. Further studies on the fluorescence properties of conjugated polymers revealed that the emission of the SDBS stabilized polymer, N-methylpolypyrrole-SDBS (NMPPY-SDBS), is strongly quenched by 2,4,6-trinitrotoluene molecule with a large Stern -Volmer constant of 59 526 M(-1) and an excellent detection limit of 100 nM. UV-vis and cyclic voltammetry measurements unveiled that fluorescence quenching occurs through a charge transfer mechanism between electron rich NMPPY-SDBS and electron deficient 2,4,6-trinitrotoluene molecules. Finally, the as-prepared conjugated polymer and approach were successfully applied to the determination of 2,4,6-trinitrotoluene in real water samples.

  11. Hybridizing Carbon Nitride Colloids with a Shell of Water-Soluble Conjugated Polymers for Tunable Full-Color Emission and Synergistic Cell Imaging.

    Science.gov (United States)

    Cui, Qianling; Xu, Jingsan; Shen, Guizhi; Zhang, Chao; Li, Lidong; Antonietti, Markus

    2017-12-20

    We present the preparation of a new multicolor emission system constructed from two complementary conjugated materials that are highly photoluminescent, that is, phenyl-modified carbon nitride (PhCN) colloids as the core and water-soluble conjugated polymers (WSCPs) adsorbed as the shell. The fluorescence bands of the PhCN and WSCPs effectively complement each other and the overall emission can be simply adjusted to fully cover the visible light spectrum with white light emission also accessible. Photophysical insights imply that the interactions between PhCN and WSCPs preserve the binary system from emission distortion and degradation, which is essential to delicately tune the overall fluorescence bands. Notably, the continuously tunable emission color is achieved under single-wavelength excitation (365 nm). This hybrid shows a synergistic permeation performance in cell imaging, that is, PhCN nanoparticles help the WSCP to enter the cells and therefore multicolor cellular imaging achieved.

  12. Water-Soluble Metallocene-Containing Polymers.

    Science.gov (United States)

    Alkan, Arda; Wurm, Frederik R

    2016-09-01

    Metallocenes are organometallic compounds with reversible redox profiles and tunable oxidation and reduction potentials, depending on the metal and substituents at the cyclopentadienyl rings. Metallocenes have been introduced in macromolecules to combine the redox-activity with polymer properties. There are many examples of such hydrophobic polymer materials, but much fewer water-soluble examples are found scattered across the polymer literature. However, in terms of drug delivery and other biological applications, water solubility is essential. For this very reason, all the synthetic routes to water-soluble metallocene containing polymers are collected and discussed here. The focus is on neutral ferrocene- and ruthenocene-containing and charged cobaltocenium-containing macromolecules (i.e., symmetrical sandwich complexes). The synthetic protocols, self-assembly behavior, and other benefits of the obtained materials are discussed. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  13. Biochemical synthesis of water soluble conducting polymers

    Energy Technology Data Exchange (ETDEWEB)

    Bruno, Ferdinando F., E-mail: Ferdinando-Bruno@uml.edu [US Army Natick Soldier Research, Development and Engineering Center, Natick, MA 01760 (United States); Bernabei, Manuele [ITAF, Test Flight Centre, Chemistry Dept. Pratica di Mare AFB, 00071 Pomezia (Rome), Italy (UE) (Italy)

    2016-05-18

    An efficient biomimetic route for the synthesis of conducting polymers/copolymers complexed with lignin sulfonate and sodium (polystyrenesulfonate) (SPS) will be presented. This polyelectrolyte assisted PEG-hematin or horseradish peroxidase catalyzed polymerization of pyrrole (PYR), 3,4 ethyldioxithiophene (EDOT) and aniline has provided a route to synthesize water-soluble conducting polymers/copolymers under acidic conditions. The UV-vis, FTIR, conductivity and cyclic voltammetry studies for the polymers/copolymer complex indicated the presence of a thermally stable and electroactive polymers. Moreover, the use of water-soluble templates, used as well as dopants, provided a unique combination of properties such as high electronic conductivity, and processability. These polymers/copolymers are nowadays tested/evaluated for antirust features on airplanes and helicopters. However, other electronic applications, such as photovoltaics, for transparent conductive polyaniline, actuators, for polypyrrole, and antistatic films, for polyEDOT, will be proposed.

  14. Water-soluble conductive polymers

    Science.gov (United States)

    Aldissi, Mahmoud

    1989-01-01

    Polymers which are soluble in water and are electrically conductive. The monomer repeat unit is a thiophene or pyrrole molecule having an alkyl group substituted for the hydrogen atom located in the beta position of the thiophene or pyrrole ring and having a surfactant molecule at the end of the alkyl chain. Polymers of this class having 8 or more carbon atoms in the alkyl chain exhibit liquid crystalline behavior, resulting in high electrical anisotropy. The monomer-to-monomer bonds are located between the carbon atoms which are adjacent to the sulfur or nitrogen atoms. The number of carbon atoms in the alkyl group may vary from 1 to 20 carbon atoms. The surfactant molecule consists of a sulfonate group, or a sulfate group, or a carboxylate group, and hydrogen or an alkali metal. Negative ions from a supporting electrolyte which may be used in the electrochemical synthesis of a polymer may be incorporated into the polymer during the synthesis and serve as a dopant to increase the conductivity.

  15. Hybrid solar cells from water-soluble polymers

    Directory of Open Access Journals (Sweden)

    James T. McLeskey

    2006-01-01

    Full Text Available We report on the use of a water-soluble, light-absorbing polythiophene polymer to fabricate novel photovoltaic devices. The polymer is a water-soluble thiophene known as sodium poly[2-(3-thienyl-ethoxy-4-butylsulfonate] or PTEBS. The intention is to take advantage of the properties of conjugated polymers (flexible, tunable, and easy to process and incorporate the additional benefits of water solubility (easily controlled evaporation rates and environmentally friendly. The PTEBS polythiophene has shown significant photovoltaic response and has been found to be effective for making solar cells. To date, solar cells in three different configurations have been produced: titanium dioxide (TiO2 bilayer cells, TiO2 bulk heterojunction solar cells, and carbon nanotubes (CNTs in bulk heterojunctions. The best performance thus far has been achieved with TiO2 bilayer devices. These devices have an open circuit voltage (Voc of 0.84V, a short circuit current (Jsc of 0.15 mA/cm2, a fill factor (ff of 0.91, and an efficiency (η of 0.15 %.

  16. Organic/Organic Cathode Bi-Interlayers Based on a Water-Soluble Nonconjugated Polymer and an Alcohol-Soluble Conjugated Polymer for High Efficiency Inverted Polymer Solar Cells.

    Science.gov (United States)

    Cai, Ping; Jia, Hongfu; Chen, Junwu; Cao, Yong

    2015-12-23

    In this work, organic/organic cathode bi-interlayers based on a water-soluble nonconjugated polymer PDMC and an alcohol-soluble conjugated polymer PFN were introduced to modifythe ITO cathode for inverted polymer solar cells (PSCs). PDMC with ultrahigh molecular weight would facilitate to form strong adsorption on the ITO substrate, while PFN could provide both compatibly interfacial contacts with the bottom PDMC interlayer and the upper organic active layer. The PDMC/PFN cathode bi-interlayers could decrease work function of the ITO cathode to 3.8 eV, supplying the most efficient ohmic interfacial contacts for electron collection at the ITO cathode. With a PTB7:PC71BM blend as the active layer, inverted PSCs based on the PDMC/PFN cathode bi-interlayers showed the highest efficiency of 9.01% and the best air stability within 60 days if compared with devices based on a separate PDMC or PFN cathode interlayer. The results suggest that the PDMC/PFN cathode bi-interlayers would play an important role to achieve high efficiency and stable inverted PSCs.

  17. Label-Free Fluorescence Assay of S1 Nuclease and Hydroxyl Radicals Based on Water-Soluble Conjugated Polymers and WS2 Nanosheets

    Directory of Open Access Journals (Sweden)

    Junting Li

    2016-06-01

    Full Text Available We developed a new method for detecting S1 nuclease and hydroxyl radicals based on the use of water-soluble conjugated poly[9,9-bis(6,6-(N,N,N-trimethylammonium-fluorene-2,7-ylenevinylene-co-alt-2,5-dicyano-1,4-phenylene] (PFVCN and tungsten disulfide (WS2 nanosheets. Cationic PFVCN is used as a signal reporter, and single-layer WS2 is used as a quencher with a negatively charged surface. The ssDNA forms complexes with PFVCN due to much stronger electrostatic interactions between cationic PFVCN and anionic ssDNA, whereas PFVCN emits yellow fluorescence. When ssDNA is hydrolyzed by S1 nuclease or hydroxyl radicals into small fragments, the interactions between the fragmented DNA and PFVCN become weaker, resulting in PFVCN being adsorbed on the surface of WS2 and the fluorescence being quenched through fluorescence resonance energy transfer. The new method based on PFVCN and WS2 can sense S1 nuclease with a low detection limit of 5 × 10−6 U/mL. Additionally, this method is cost-effective by using affordable WS2 as an energy acceptor without the need for dye-labeled ssDNA. Furthermore, the method provides a new platform for the nuclease assay and reactive oxygen species, and provides promising applications for drug screening.

  18. Water-Soluble Conjugated Polymer as a Fluorescent Probe for Monitoring Adenosine Triphosphate Level Fluctuation in Cell Membranes during Cell Apoptosis and in Vivo.

    Science.gov (United States)

    Huang, Binghuan; Geng, Zhirong; Yan, Shihai; Li, Zan; Cai, Jun; Wang, Zhilin

    2017-09-05

    Adenosine triphosphate (ATP) is used as the energy source in cells and plays crucial roles in various cellular events. The cellular membrane is the protective barrier for the cytoplasm of living cells and involved in many essential biological processes. Many fluorescent probes for ATP have been successfully developed, but few of these probes were appropriate for visualizing ATP level fluctuation in cell membranes during the apoptotic cell death process. Herein, we report the synthesis of a new water-soluble cationic polythiophene derivative that can be utilized as a fluorescent sensor for detecting ATP in cell membranes. Poly((3-((4-methylthiophen-3-yl)oxy)propyl)triphenylphosphonium chloride) (PMTPP) exhibits high sensitivity and good selectivity to ATP, and the detection limit is 27 nM. The polymer shows low toxicity to live cells and excellent photostability in cell membranes. PMTPP was practically utilized for real-time monitoring of ATP levels in the cell membrane through fluorescence microscopy. We have demonstrated that the ATP levels in cell membranes increased during the apoptotic cell death process. The probe was also capable of imaging ATP levels in living mice.

  19. Application of various water soluble polymers in gas hydrate inhibition

    DEFF Research Database (Denmark)

    Kamal, Muhammad Shahzad; Hussein, Ibnelwaleed A.; Sultan, Abdullah S.

    2016-01-01

    . This review presents the various types of water soluble polymers used for hydrate inhibition, including conventional and novel polymeric inhibitors along with their limitations. The review covers the relevant properties of vinyl lactam, amide, dendrimeric, fluorinated, and natural biodegradable polymers....... The factors affecting the performance of these polymers and the structure-property relationships are reviewed. A comprehensive review of the techniques used to evaluate the performance of the polymeric inhibitors is given. This review also addresses recent developments, current and future challenges......, and field applications of a range of polymeric kinetic hydrate inhibitors....

  20. Reactivity of Metal Ions Bound to Water-Soluble Polymers

    Energy Technology Data Exchange (ETDEWEB)

    Sauer, N.N.; Watkins, J.G.; Lin, M.; Birnbaum, E.R.; Robison, T.W.; Smith, B.F.; Gohdes, J.W.; McDonald, J.G.

    1999-06-29

    The intent of this work is to determine the effectiveness of catalysts covalently bound to polymers and to understand the consequences of supporting the catalysts on catalyst efficiency and selectivity. Rhodium phosphine complexes with functional groups for coupling to polymers were prepared. These catalyst precursors were characterized using standard techniques including IR, NMR, and elemental analysis. Studies on the modified catalysts showed that they were still active hydrogenation catalysts. However, tethering of the catalysts to polyamines gave systems with low hydrogenation activity. Analogous biphasic systems were also explored. Phosphine ligands with a surfactant-like structure have been synthesized and used to prepare catalytically active complexes of palladium. The palladium complexes were utilized in Heck-type coupling reactions (e.g. coupling of iodobenzene and ethyl acrylate to produce ethyl cinnamate) under vigorously stirred biphasic reaction conditions, and were found to offer superior performance over a standard water-soluble palladium catalyst under analogous conditions.

  1. Water Soluble Polymers as Proton Exchange Membranes for Fuel Cells

    Directory of Open Access Journals (Sweden)

    Bing-Joe Hwang

    2012-03-01

    Full Text Available The relentless increase in the demand for useable power from energy-hungry economies continues to drive energy-material related research. Fuel cells, as a future potential power source that provide clean-at-the-point-of-use power offer many advantages such as high efficiency, high energy density, quiet operation, and environmental friendliness. Critical to the operation of the fuel cell is the proton exchange membrane (polymer electrolyte membrane responsible for internal proton transport from the anode to the cathode. PEMs have the following requirements: high protonic conductivity, low electronic conductivity, impermeability to fuel gas or liquid, good mechanical toughness in both the dry and hydrated states, and high oxidative and hydrolytic stability in the actual fuel cell environment. Water soluble polymers represent an immensely diverse class of polymers. In this comprehensive review the initial focus is on those members of this group that have attracted publication interest, principally: chitosan, poly (ethylene glycol, poly (vinyl alcohol, poly (vinylpyrrolidone, poly (2-acrylamido-2-methyl-1-propanesulfonic acid and poly (styrene sulfonic acid. The paper then considers in detail the relationship of structure to functionality in the context of polymer blends and polymer based networks together with the effects of membrane crosslinking on IPN and semi IPN architectures. This is followed by a review of pore-filling and other impregnation approaches. Throughout the paper detailed numerical results are given for comparison to today’s state-of-the-art Nafion® based materials.

  2. Water-soluble, electroactive, and photoluminescent quaterthiophene-dinucleotide conjugates.

    Science.gov (United States)

    Alesi, Silvia; Brancolini, Giorgia; Melucci, Manuela; Capobianco, Massimo Luigi; Venturini, Alessandro; Camaioni, Nadia; Barbarella, Giovanna

    2008-01-01

    Quaterthiophene-dinucleotide conjugates 5'TA3'-t4-3'AT5', 5'AA3'-t4-3'AA5', and 5'TT3'-t4-3'TT5' (TA: thymidine-adenosine, AA: adenosine-adenosine, TT: thymidine-thymidine) were synthesized and analyzed by a combination of spectroscopy and microscopy, electrical characterization, and theoretical calculations. Circular dichroism (CD) experiments demonstrated a transfer of chirality from the dinucleotides to quaterthiophene at high ionic strength and in cast films. The films were photoluminescent and electroactive. CD and photoluminescence spectra and current density/voltage plots (measured under dynamic vacuum) displayed significant variation on changing the dinucleotide scaffold. Molecular mechanics and molecular dynamics calculations indicated that the conformation and packing modes of the conjugates are the result of a balance between intra- and intermolecular nucleobase-thiophene stacking interactions and intramolecular hydrogen bonding between the nucleobases.

  3. Water-soluble dopamine-based polymers for photoacoustic imaging

    NARCIS (Netherlands)

    Repenko, T.; Fokong, S.; De Laporte, L.; Go, D.; Kiessling, F.; Lammers, Twan Gerardus Gertudis Maria; Kuehne, A.

    2015-01-01

    Here we present a facile synthetic method yielding a linear form of polydopamine via Kumada-coupling, which can be converted into water-soluble melanin, generating high contrast in photoacoustic imaging.

  4. Fluorescent polystyrene photonic crystals self-assembled with water-soluble conjugated polyrotaxanes

    Directory of Open Access Journals (Sweden)

    Francesco Di Stasio

    2013-10-01

    Full Text Available We demonstrate control of the photoluminescence spectra and decay rates of water-soluble green-emitting conjugated polyrotaxanes by incorporating them in polystyrene opals with a stop-band spectrally tuned on the rotaxane emission (405–650 nm. We observe a suppression of the luminescence within the photonic stop-band and a corresponding enhancement of the high-energy edge (405–447 nm. Time-resolved measurements reveal a wavelength-dependent modification of the emission lifetime, which is shortened at the high-energy edge (by ∼11%, in the range 405–447 nm, but elongated within the stop-band (by ∼13%, in the range 448–482 nm. We assign both effects to the modification of the density of photonic states induced by the photonic crystal band structure. We propose the growth of fluorescent composite photonic crystals from blends of “solvent-compatible” non-covalently bonded nanosphere-polymer systems as a general method for achieving a uniform distribution of polymeric dopants in three-dimensional self-assembling photonic structures.

  5. Solubilization of poorly water-soluble compounds using amphiphilic phospholipid polymers with different molecular architectures.

    Science.gov (United States)

    Mu, Mingwei; Konno, Tomohiro; Inoue, Yuuki; Ishihara, Kazuhiko

    2017-10-01

    To achieve stable and effective solubilization of poorly water-soluble bioactive compounds, water-soluble and amphiphilic polymers composed of hydrophilic 2-methacryloyloxyethyl phosphorylcholine (MPC) units and hydrophobic n-butyl methacrylate (BMA) units were prepared. MPC polymers having different molecular architectures, such as random-type monomer unit sequences and block-type sequences, formed polymer aggregates when they were dissolved in aqueous media. The structure of the random-type polymer aggregate was loose and flexible. On the other hand, the block-type polymer formed polymeric micelles, which were composed of very stable hydrophobic poly(BMA) cores and hydrophilic poly(MPC) shells. The solubilization of a poorly water-soluble bioactive compound, paclitaxel (PTX), in the polymer aggregates was observed, however, solubilizing efficiency and stability were strongly depended on the polymer architecture; in other words, PTX stayed in the poly(BMA) core of the polymer micelle formed by the block-type polymer even when plasma protein was present in the aqueous medium. On the other hand, when the random-type polymer was used, PTX was transferred from the polymer aggregate to the protein. We conclude that water-soluble and amphiphilic MPC polymers are good candidates as solubilizers for poorly water-soluble bioactive compounds. Copyright © 2017 Elsevier B.V. All rights reserved.

  6. Heterophase Photocatalysts from Water-Soluble Conjugated Polyelectrolytes: An Example of Self-Initiation under Visible Light.

    Science.gov (United States)

    Ghasimi, Saman; Prescher, Simon; Wang, Zi Jun; Landfester, Katharina; Yuan, Jiayin; Zhang, Kai A I

    2015-11-23

    We herein report a new design route to stable, heterophase photocatalysts, which function as highly dispersible conjugated polymer nanoparticles and porous monoliths under visible light in aqueous medium. They were constructed by attachment of the ionic-liquid species 1-alkyl-3-vinylimidazolium bromide onto the side chains of a photoactive polymer. The structure configuration allows not only photocatalysis in aqueous environment but also a unique self-initiation radical cross-linking process to transform the water-soluble photoactive polymer into a heterophase system, either as nanoparticles or a porous monolith. High photocatalytic activity and reusability of the heterophase system were demonstrated in the degradation of organic dyes and reduction of Cr(VI) into Cr(III) in water under visible-light irradiation. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. Preparation of the Water-Soluble Pyrene-Containing Fluorescent Polymer by One-Pot Method

    Directory of Open Access Journals (Sweden)

    Xiaomeng Li

    2015-12-01

    Full Text Available A new water-soluble pyrene-containing fluorescent polymer, 1-{3′-S-[poly(acryloyl ethylene diamine hydrochloride-2′-methyl propionic acid]}propionyloxy hexyloxy pyrene (P3 with defined structure, was designed and synthesized using the click reaction between thiol and a carbon-carbon double bond. The intermediate products P1 (S-1-dodecyl-S′-[poly(N-Boc-acryloyl ethylene diamine-2′-methyl propionic acid]trithiocarbonate and AHP (1-(acryloyloxy hexyloxypyrene were prepared via reversible addition fragmentation chain transfer (RAFT polymerization and Williamson synthesis, respectively. Conjugating AHP with P1, P2 (1-{3′-S-[poly(N-butoxycarbonyl-acryloyl ethylene diamine-2″-methyl propionic acid]} propionyloxy hexyloxy pyrene was synthesized, adopting both the reduction reaction of a trithioester bond of P1 to thiol and the click reaction between thiol and the carbon-carbon double bond of AHP simultaneously. P3 was obtained by the deprotection of the resulting Boc-protected polymer (P2 with aqueous HCl. The experiment results showed that P2 exhibited a bright blue-violet emission band at approximately 387–429 nm. After deprotection, P3 displayed good solubility in water and not only exhibited a blue-violet fluorescence emission band at approximately 387–429 nm in aqueous solution but also had the similar photoluminescent spectra to those of AHP and P2 in dichloromethane. The fluorescence quantum yields of P2 in dilute tetrahydrofuran and P3 in a dilute aqueous solution were 0.44 and 0.39, respectively. This experiment provided a novel insight into the study of water-soluble fluorescent polymers.

  8. Synthesis and biological evaluation of new water-soluble photoactive chlorin conjugate for targeted delivery.

    Science.gov (United States)

    Otvagin, Vasilii F; Nyuchev, Alexander V; Kuzmina, Natalia S; Grishin, Ivan D; Gavryushin, Andrei E; Romanenko, Yuliya V; Koifman, Oscar I; Belykh, Dmitrii V; Peskova, Nina N; Shilyagina, Natalia Yu; Balalaeva, Irina V; Fedorov, Alexey Yu

    2018-01-20

    A new water-soluble conjugate, consisting of a chlorin-based photosensitizing part, and a 4-arylaminoquinazoline moiety with high potential affinity to an epidermal growth factor receptors (EGFR) and vascular endothelial growth factor receptors (VEGFR), suitable for photodynamic therapy (PDT), was synthesized starting from methylpheophorbide-a in seven steps. An increased accumulation of this compound in A431 cells with high level of EGFR expression, in comparison with CHO and HeLa cells with low EGFR expression was observed. The prepared conjugate exhibits dark and photoinduced cytotoxicity at micromolar concentrations with IC 50dark /IC 50light ratio of 11-18. In tumor-bearing mice, the conjugate preferentially accumulates in the tumor tissue. Copyright © 2017 Elsevier Masson SAS. All rights reserved.

  9. Synthesis and photophysicochemical studies of a water soluble conjugate between folic acid and zinc tetraaminophthalocyanine

    Energy Technology Data Exchange (ETDEWEB)

    Khoza, Phindile; Antunes, Edith [Department of Chemistry, Rhodes University, PO Box 94, Grahamstown (South Africa); Chen, Ji-Yao [State Key Laboratory of Surface Physics and Department of Physics, Fudan University, Shanghai 200433 (China); Nyokong, Tebello, E-mail: t.nyokong@ru.ac.za [Department of Chemistry, Rhodes University, PO Box 94, Grahamstown (South Africa)

    2013-02-15

    This work reports on the synthesis of zinc tetraaminophthalocyanine (ZnTAPc) functionalized with folic acid (FA), forming ZnTAPcFA. The conjugate between FA and ZnTAPc was soluble in water whereas ZnTAPc alone is not. The structure of ZnTAPcFA conjugate was elucidated by {sup 1}H NMR, MALDI-TOF mass and FTIR spectra. Photophysical and photochemical studies of ZnTAPcFA were conducted in DMSO. The increase in fluorescence quantum yield of the conjugate was accompanied by a decrease in the triplet and singlet oxygen quantum yields. The changes in triplet quantum and singlet oxygen quantum yields were marginal when ZnTAPc was simply mixed with FA without a chemical bond. - Highlights: Black-Right-Pointing-Pointer A conjugate between folic acid and a zinc tetraaminophthalocyanine was formed. Black-Right-Pointing-Pointer The conjugate is water soluble even though the phthalocyanine alone is not. Black-Right-Pointing-Pointer The fluorescence quantum yield of the conjugate was enhanced compared to the phthalocyanine alone. Black-Right-Pointing-Pointer Triplet quantum yields decreased for the conjugate.

  10. Polymer-assisted synthesis of water-soluble PbSe quantum dots

    Energy Technology Data Exchange (ETDEWEB)

    Melnig, V., E-mail: vmelnig@uaic.r [' Al. I. Cuza' University, Faculty of Physics (Romania); Apostu, M.-O. [' Al. I. Cuza' University, Faculty of Chemistry (Romania); Foca, N. [' Gh. Asachi' University, Faculty of Chemistry (Romania)

    2008-12-15

    Stable PbSe quantum dots were synthesised in water-based media using poly(amidehydroxyurethane) water-soluble polymer. The polymer acts like a precursor carrier, blocks the particles aggregation and assures their solubility. Atomic force microscopy data show that the particle radius is smaller than the Bohr radius of PbSe. Interactions studies, performed by Fourier transform IR spectroscopy, show that the quantum dots are capped with poly(amidehydroxyurethane). The proposed synthesis was realised in the absence of any organic solvent. As a result, the produced particles have good water solubility, stability and good arguments to be biologically compatible.

  11. Fluorescent water soluble polymers for isozyme-selective interactions with matrix metalloproteinase-9.

    Science.gov (United States)

    Dutta, Rinku; Scott, Michael D; Haldar, Manas K; Ganguly, Bratati; Srivastava, D K; Friesner, Daniel L; Mallik, Sanku

    2011-04-01

    Matrix metalloproteinases (MMPs) are overexpressed in various pathological conditions, including cancers. Although these isozymes have similar active sites, the patterns of exposed amino acids on their surfaces are different. Herein, we report the synthesis and molecular interactions of two water soluble, fluorescent polymers which demonstrate selective interactions with MMP-9 compared to MMP-7 and -10. Copyright © 2011 Elsevier Ltd. All rights reserved.

  12. INTERACTIONS BETWEEN WATER-SOLUBLE NONIONIC POLYMERS AND SURFACTANT AGGREGATES

    NARCIS (Netherlands)

    BRACKMAN, JC; ENGBERTS, JBFN; Herb, CA; Prudhomme, RK

    1994-01-01

    The influence of the chemical structure and charge of the surfactant on polymer-micelle interaction has been studied using various ionic and non-ionic surfactants, and surfactants of which the charge can be varied by (de)protonation. Octylthioglucoside, dodecyldimethylamine-oxide, alkylphosphates,

  13. Synthesis and Biological Evaluation of Novel Water-Soluble Poly-(ethylene glycol-10-hydroxycamptothecin Conjugates

    Directory of Open Access Journals (Sweden)

    Na Guo

    2015-05-01

    Full Text Available In order to improve the antitumor activity and water solubility of 10-hydroxycamptothecin (HCPT, a series of novel HCPT conjugates were designed and synthesized by conjugating polyethylene glycol (PEG to the 10-hydroxyl group of HCPT via a valine spacer. The in vitro stability of these synthesized compounds was determined in pH 7.4 buffer at 37 °C, and the results showed that they released HCPT at different rates. All the compounds demonstrated significant antitumor activity in vitro against K562, HepG2 and HT-29 cells. Among them, compounds, 4a, 4d, 4e and 4f, exhibited 2–5 times higher potency than HCPT. The stability and antitumor activity of these conjugates were found to be closely related to the length of PEG and the linker type, conjugates with a relatively short PEG chain and carbamate linkages (compounds 4a and 4f exhibited controlled release of HCPT and excellent antitumor in vitro activity.

  14. Segmented conjugated polymers

    Indian Academy of Sciences (India)

    Abstract. Segmented conjugated polymers, wherein the conjugation is randomly truncated by varying lengths of non-conjugated segments, form an interesting class of polymers as they not only represent systems of varying stiffness, but also ones where the backbone can be construed as being made up of chromophores of ...

  15. Segmented conjugated polymers

    Indian Academy of Sciences (India)

    Segmented conjugated polymers, wherein the conjugation is randomly truncated by varying lengths of non-conjugated segments, form an interesting class of polymers as they not only represent systems of varying stiffness, but also ones where the backbone can be construed as being made up of chromophores of varying ...

  16. A water-soluble triiodo amino acid and its dendrimer conjugate for computerized tomography (CT imaging

    Directory of Open Access Journals (Sweden)

    MARTIN W. BRECHBIEL

    2005-02-01

    Full Text Available Prolonging the circulation of an imaging agent is vital for making it suitable for blood pool (vascular imaging. Medical applications of vascular imaging include cardiovascular disease, abnormal capillary permeability, and tumor neovascularity. As low molecular weight computerized tomography (CT enhancement agents are characterized by inconveniently fast clearance, macromolecular compounds (both natural and synthetic have gained a wide recongnition for possessing better characteristics for performing blood imaging tasks. Herein, the syntheses and characterization of a new water-soluble triiodo amino acid, 3-[(N,N-dimethylaminoacetyl amino]-a-ethyl-2,4,6-triiodobenzenepropanoic acid (DMAA-IPA and its Starburst PAMAMgeneration 4.0 dendrimer conjugate, G-4-(DMAA-IPA37 are described. The applicability of G-4-(DMAA-IPA37 as a potential macromolecular angiographic CT contrast agent is discussed. The linear relationship between organically bound iodine concentration and CT Hounsfield units has been established thus allowing for quantification uses of CT imaging as well.

  17. Synthesis, structure, antioxidant activity, and water solubility of trolox ion conjugates

    Directory of Open Access Journals (Sweden)

    Yuliya V. Yushkova

    2018-01-01

    Full Text Available The interaction of trolox with ammonia, alkylamines of different classes, and amino derivatives of heterocyclic compounds, including nitroxyl radicals and alkaloids, led to the production of ammonium salts called ion conjugates (ICs. Five ICs were characterised by X-ray diffraction. This is the first time a wide range of ICs were made from trolox with amines, and ESI-MS data demonstrated they have the potential to generate pseudomolecular [(A−B+ + H]+ ions. For all obtained trolox ICs, a significant increase (1–3 orders of magnitude in water solubility was achieved while retaining high antioxidant activity. ICs synthesised from two biologically active fragments may be used to create polyfunctional agents with varying solubility and bioavailability.

  18. Water-soluble chelating polymers for removal of actinides from watewater

    Energy Technology Data Exchange (ETDEWEB)

    Jarvinen, G. [Los Alamos National Lab., NM (United States)

    1996-10-01

    Polymer filtration is a technology being developed to recover valuable or regulated metal ions selectively from process or wastewaters. Water-soluble chelating polymers are specially designed to bind selectively with metal ions in aqueous solutions. The polymers molecular weight is large enough so they can be separated and concentrated using available ultrafiltration technology. Water and smaller unbound components of the solution pass freely through the ultrafiltration membrane. The polymers can then be reused by changing the solution conditions to release the metal ions, which are recovered in concentrated form, for recycle or disposal.

  19. Synthesis and characterization of a hyper-branched water-soluble β-cyclodextrin polymer.

    Science.gov (United States)

    Trotta, Francesco; Caldera, Fabrizio; Cavalli, Roberta; Mele, Andrea; Punta, Carlo; Melone, Lucio; Castiglione, Franca; Rossi, Barbara; Ferro, Monica; Crupi, Vincenza; Majolino, Domenico; Venuti, Valentina; Scalarone, Dominique

    2014-01-01

    A new hyper-branched water-soluble polymer was synthesized by reacting β-cyclodextrin with pyromellitic dianhydride beyond the critical conditions that allow the phenomenon of gelation to occur. The molar ratio between the monomers is a crucial parameter that rules the gelation process. Nevertheless, the concentration of monomers in the solvent phase plays a key role as well. Hyper-branched β-cyclodextrin-based polymers were obtained performing the syntheses with excess of solvent and cross-linking agent, and the conditions for critical dilution were determined experimentally. A hyper-branched polymer with very high water solubility was obtained and fully characterized both as for its chemical structure and for its capability to encapsulate substances. Fluorescein was used as probe molecule to test the complexation properties of the new material.

  20. Synthesis and characterization of a hyper-branched water-soluble β-cyclodextrin polymer

    Directory of Open Access Journals (Sweden)

    Francesco Trotta

    2014-11-01

    Full Text Available A new hyper-branched water-soluble polymer was synthesized by reacting β-cyclodextrin with pyromellitic dianhydride beyond the critical conditions that allow the phenomenon of gelation to occur. The molar ratio between the monomers is a crucial parameter that rules the gelation process. Nevertheless, the concentration of monomers in the solvent phase plays a key role as well. Hyper-branched β-cyclodextrin-based polymers were obtained performing the syntheses with excess of solvent and cross-linking agent, and the conditions for critical dilution were determined experimentally. A hyper-branched polymer with very high water solubility was obtained and fully characterized both as for its chemical structure and for its capability to encapsulate substances. Fluorescein was used as probe molecule to test the complexation properties of the new material.

  1. Poly(ether ester) Ionomers as Water-Soluble Polymers for Material Extrusion Additive Manufacturing Processes.

    Science.gov (United States)

    Pekkanen, Allison M; Zawaski, Callie; Stevenson, André T; Dickerman, Ross; Whittington, Abby R; Williams, Christopher B; Long, Timothy E

    2017-04-12

    Water-soluble polymers as sacrificial supports for additive manufacturing (AM) facilitate complex features in printed objects. Few water-soluble polymers beyond poly(vinyl alcohol) enable material extrusion AM. In this work, charged poly(ether ester)s with tailored rheological and mechanical properties serve as novel materials for extrusion-based AM at low temperatures. Melt transesterification of poly(ethylene glycol) (PEG, 8k) and dimethyl 5-sulfoisophthalate afforded poly(ether ester)s of sufficient molecular weight to impart mechanical integrity. Quantitative ion exchange provided a library of poly(ether ester)s with varying counterions, including both monovalent and divalent cations. Dynamic mechanical and tensile analysis revealed an insignificant difference in mechanical properties for these polymers below the melting temperature, suggesting an insignificant change in final part properties. Rheological analysis, however, revealed the advantageous effect of divalent countercations (Ca 2+ , Mg 2+ , and Zn 2+ ) in the melt state and exhibited an increase in viscosity of two orders of magnitude. Furthermore, time-temperature superposition identified an elevation in modulus, melt viscosity, and flow activation energy, suggesting intramolecular interactions between polymer chains and a higher apparent molecular weight. In particular, extrusion of poly(PEG 8k -co-CaSIP) revealed vast opportunities for extrusion AM of well-defined parts. The unique melt rheological properties highlighted these poly(ether ester) ionomers as ideal candidates for low-temperature material extrusion additive manufacturing of water-soluble parts.

  2. First water-soluble backbone Ru-Ru-Ni heterometallic organometallic polymer.

    Science.gov (United States)

    Scalambra, Franco; Serrano-Ruiz, Manuel; Romerosa, Antonio

    2015-04-01

    The water-soluble backbone heterometallic polymer {[(PTA)2 CpRu-μ-CN-RuCp(PTA)2 -μ-NiCl3 ]}n (2) is synthesized using a reproducible and robust method and fully characterized by X-ray single crystal diffraction. The Ru-Ru-Ni polymer is found to be stable in the solid state and soluble in water. Nuclear magnetic resonance (NMR) and light scattering studies show that the polymer is stable in water for several days in air. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. Water soluble polymer protected lipofectamine 2000/DNA complexes for solid-phase transfection.

    Science.gov (United States)

    Zhang, Qiao; Cheng, Si-Xue; Zhang, Xian-Zheng; Zhuo, Ren-Xi

    2009-12-08

    A fast degrading cholic acid-functionalized star poly(DL-lactide) has been used to fabricate polymer films to support Lipofectamine 2000/DNA complexes for mediating solid-phase transfection. To improve the gene expression activity, a water-soluble polymer, poly-alpha,beta-[N-(2-hydroxyethyl)-L-aspartamide (PHEA), was added to protect the complexes. The in vitro gene transfection in 293T cells, HeLa cells, and 3T3 cells showed that the gene expressions could be effectively mediated by the deposited Lipofectamine 2000/DNA complexes encapsulated in polymer films. The degradation of the polymer films that occurred during gene transfection did not show any unfavorable effects on the gene expression.

  4. 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.

  5. Effect of sodium dodecyl benzene sulfonate on water-soluble hydrophobically associating polymer solutions

    Energy Technology Data Exchange (ETDEWEB)

    Zhou, W.; Dong, M. [University of Regina, Faculty of Engineering, Regina, SK (Canada); Guo, Y. [Southwest Petroleum Institute (China); Xiao, H. [University of New Brunswick, Dept. of Chemical Engineering, Fredericton, NB (Canada)

    2004-02-01

    Water-soluble polymers are widely used in oilfield operations such as drilling, flooding and profile modification. Using the fluorescence probe approach, this paper investigates the effect of sodium dodecyl benzene (SDBS) on the rheological characteristics of the modified hydrophobically associated polymer (HAP) aqueous solutions. Polymer surfactant interactions and formations of hydrophobic domains are also investigated. Results show that the presence of SDBS enhances the structure viscosity of the polymer solution and causes a competition between intra- and intermolecular interaction. Low concentration of SDBS resulted in the cross-linkage of the hydrophobic groups of polymers; high concentrations of SDBS tended to disrupt the associated structures. Fluorescent results showed the ability of SDBS to provide information on the microstructure of solutions, including the generation of microdomains which strengthened the viscosity of the polymer solutions. In low shear rate range, and with SDBS concentration of about 1.0x10{sup 3} mol/L, the polymer solution exhibited significant shear thickening when the HAP concentration ranged from a dilute regime to an entangled semi-dilute regime. Beyond this level of SDBS, the viscosity of the polymer decreased, due to the SDBS molecules inhibiting interactions between polymers by forming micelles around the hydrophobes, causing the disappearance of the intermolecular association, and the disruption of the cross-linking structure. It was concluded that with an achievable high viscosity this system showed high promise as an effective thickener for enhanced oil recovery. 10 refs., 4 figs.

  6. Water-soluble chelating polymers for removal of actinides from wastewater

    Energy Technology Data Exchange (ETDEWEB)

    Jarvinen, G.D. [Los Alamos National Lab., NM (United States)

    1997-10-01

    Polymer filtration is a technology under development to selectively recover valuable or regulated metal ions from process or wastewaters. The technology uses water-soluble chelating polymers that are designed to selectively bind with metal ions in aqueous solutions. The polymers have a sufficiently large molecular weight that they can be separated and concentrated using available ultrafiltration (UF) technology. The UF range is generally considered to include molecular weights from about 3000 to several million daltons and particles sizes of about 2 to 1000 nm. Water and smaller unbound components of the solution pass freely through the UF membrane. The polymers can then be reused by changing the solution conditions to release the metal ions that are recovered in concentrated form for recycle or disposal. Some of the advantages of polymer filtration relative to technology now in use are rapid binding kinetics, high selectivity, low energy and capital costs, and a small equipment footprint. Some potential commercial applications include electroplating rinse waters, photographic processing, nuclear power plant cooling water; remediation of contaminated soils and groundwater; removal of mercury contamination; and textile, paint and dye production. The purpose of this project is to evaluate this technology to remove plutonium, americium, and other regulated metal ions from various process and waste streams found in nuclear facilities. The work involves preparation of the water-soluble chelating polymers; small-scale testing of the chelating polymer systems for the required solubility, UF properties, selectivity and binding constants; followed by an engineering assessment at a larger scale to allow comparison to competing separation technologies. This project focuses on metal-ion contaminants in waste streams at the Plutonium Facility and the Waste Treatment Facility at LANL. Potential applications at other DOE facilities are also apparent.

  7. Enzymatic synthesis of a 6-sialyl lactose analogue using a pH-responsive water-soluble polymer support.

    Science.gov (United States)

    Wang, Wenjun; Li, Lei; Jin, Chen; Niu, Yujie; Li, Sen; Ma, Ji; Li, Linfeng; Liu, Yu; Cai, Li; Zhao, Wei; Wang, Peng George

    2011-09-01

    The Letter describes a strategy for the enzymatic synthesis of glycans based on a pH-responsive water-soluble polymer. In neutral condition, the polymer is water-soluble and convenient for in-solution enzymatic synthesis, whereas in acidic condition (pH lower than 4.0), the polymer disconnects with the product and becomes insoluble, which can be easily removed. A 6-Sialyl lactose analogue was synthesized as a model reaction using this approach. Copyright © 2011. Published by Elsevier Ltd.

  8. Salting-in and salting-out of water-soluble polymers in aqueous salt solutions.

    Science.gov (United States)

    Sadeghi, Rahmat; Jahani, Farahnaz

    2012-05-03

    To obtain further experimental evidence for the mechanisms of the salting effect produced by the addition of salting-out or sating-in inducing electrolytes to aqueous solutions of water-soluble polymers, systematic studies on the vapor-liquid equilibria and liquid-liquid equilibria of aqueous solutions of several polymers are performed in the presence of a large series of electrolytes. Polymers are polyethylene glycol 400 (PEG400), polyethylene glycol dimethyl ether 250 (PEGDME250), polyethylene glycol dimethyl ether 2000 (PEGDME2000), and polypropylene glycol 400 (PPG400), and the investigated electrolytes are KCl, NH(4)Cl, MgCl(2), (CH(3))(4)NCl, NaCl, NaNO(3), Na(2)CO(3), Na(2)SO(4), and Na(3)Cit (tri-sodium citrate). Aqueous solutions of PPG400 form aqueous two-phase systems with all the investigated salts; however, other investigated polymers form aqueous two-phase systems only with Na(2)CO(3), Na(2)SO(4), and Na(3)Cit. A relation was found between the salting-out or sating-in effects of electrolyte on the polymer aqueous solutions and the slopes of the constant water activity lines of ternary polymer-salt aqueous solutions, so that, in the case of the salting-out effect, the constant water activity lines had a concave slope, but in the case of the salting-in effects, the constant water activity lines had a convex slope. The effect of temperature, anion of electrolyte, cation of electrolyte, and type and molar mass of polymers were studied and the results interpreted in terms of the solute-water and solute-solute interactions. The salting-out effect results from the formation of ion (specially anion)-water hydration complexes, which, in turn, decreases hydration, and hence, the solubility of the polymer and the salting-in effect results from a direct binding of the cations to the ether oxygens of the polymers.

  9. Size-Dependent Photodynamic Activity of Gold Nanoparticles Conjugate of Water Soluble Purpurin-18-N-Methyl-D-Glucamine

    Directory of Open Access Journals (Sweden)

    Byambajav Lkhagvadulam

    2013-01-01

    Full Text Available Gold nanoparticles (GNPs conjugates of water soluble ionic photosensitizer (PS, purpurin-18-N-methyl-D-glucamine (Pu-18-NMGA, were synthesized using various molar ratios between HAuCl4 and Pu-18-NMGA without adding any particular reducing agents and surfactants. The PS-GNPs conjugates showed long wavelength absorption of range 702–762 nm, and their different shapes and diameters depend on the molar ratios used in the synthesis. In vitro anticancer efficacy of the PS-GNPs conjugates was investigated by MTT assay against A549 cells, resulting in higher photodynamic activity than that of the free Pu-18-NMGA. Among the PS-GNPs conjugates, the GNPs conjugate from the molar ratio of 1 : 2 (Au(III: Pu-18-NMGA exhibits the highest photodynamic activity corresponding to bigger size (~60 nm of the GNPs conjugate which could efficiently transport the PS into the cells than that of smaller size of the GNPs conjugate.

  10. Radiation crosslinking of starch/water-soluble polymer blends for hydrogel

    Energy Technology Data Exchange (ETDEWEB)

    Hashim, K.; Mohid, N.; Bahari, K.; Dahlan, K.Z. [Radiation Processing Technology Division, Malaysian Institute Nuclear Technology Research Malaysia (MINT), Bangi, 43000 Kajang (Malaysia)

    2000-03-01

    Water-soluble polymers such as PVP(polyvinyl pyrrolidone) and PVA(polyvinyl alcohol), in aqueous solution can form hydrogel easily upon gamma or electron beam irradiation. The properties of hydrogels, particularly for wound dressing application, can be further improved by adding sago starch to the blend. Results show improved gel strength and elongation properties of the hydrogel with increasing sago concentration. It was found that the PVA/sago hydrogel gives better gel strength and elongation than the PVP/sago hydrogel. The tackiness property of the PVA/sago hydrogel increased with increase amount of sago starch added. In case of PVP/sago hydrogel, the tackiness property shows significant increase with increasing amount of sago except for the 5%PVP composition. The swelling properties of PVP/sago and PVA/sago hydrogel decreased with increasing amount of sago but the crosslink density of the hydrogels also reduced. (author)

  11. From Cooperative Self-Assembly to Water-Soluble Supramolecular Polymers Using Coarse-Grained Simulations.

    Science.gov (United States)

    Bochicchio, Davide; Pavan, Giovanni M

    2017-01-24

    Supramolecular polymers, formed via noncovalent self-assembly of elementary monomers, are extremely interesting for their dynamic bioinspired properties. In order to understand their behavior, it is necessary to access their dynamics while maintaining high resolution in the treatment of the monomer structure and monomer-monomer interactions, which is typically a difficult task, especially in aqueous solution. Focusing on 1,3,5-benzenetricarboxamide (BTA) water-soluble supramolecular polymers, we have developed a transferable coarse-grained model that allows studying BTA supramolecular polymerization in water, while preserving remarkable consistency with the atomistic models in the description of the key interactions between the monomers (hydrophobic, H-bonding, etc.), self-assembly cooperativity, and amplification of order into the growing fibers. This permitted us to monitor the amplification of the key interactions between the monomers (including H-bonding) in the BTA fibers during the dynamic polymerization process. Our molecular dynamics simulations provide a picture of a stepwise cooperative polymerization mechanism, where initial fast hydrophobic aggregation of the BTA monomers in water is followed by the slower reorganization of these disordered aggregates into ordered directional oligomers. Supramolecular polymer growth then proceeds on a slower time scale. We challenged our models via comparison with the experimental evidence, capturing the effect of temperature variations and subtle changes in the monomer structure on the polymerization and on the properties of the fibers seen in the real systems. This work provides a multiscale spatiotemporal characterization of BTA self-assembly in water and a useful platform to study a variety of BTA-based supramolecular polymers toward structure-property relationships.

  12. Water-soluble polymer–drug conjugates for combination chemotherapy against visceral leishmaniasis

    Science.gov (United States)

    Nicoletti, Salvatore; Seifert, Karin; Gilbert, Ian H.

    2010-01-01

    There is a need for new safe, effective and short-course treatments for leishmaniasis; one strategy is to use combination chemotherapy. Polymer–drug conjugates have shown promise for the delivery of anti-leishmanial agents such as amphotericin B. In this paper, we report on the preparation and biological evaluation of polymer–drug conjugates of N-(2-hydroxypropyl)methacrylamide (HPMA), amphotericin B and alendronic acid. The combinatorial polymer–drug conjugates were effective anti-leishmanial agents in vitro and in vivo, but offered no advantage over the single poly(HPMA)–amphotericin B conjugates. PMID:20338769

  13. Towards improved solubility of poorly water-soluble drugs: cryogenic co-grinding of piroxicam with carrier polymers.

    Science.gov (United States)

    Penkina, Anna; Semjonov, Kristian; Hakola, Maija; Vuorinen, Sirpa; Repo, Timo; Yliruusi, Jouko; Aruväli, Jaan; Kogermann, Karin; Veski, Peep; Heinämäki, Jyrki

    2016-01-01

    Amorphous solid dispersions (SDs) open up exciting opportunities in formulating poorly water-soluble active pharmaceutical ingredients (APIs). In the present study, novel catalytic pretreated softwood cellulose (CPSC) and polyvinylpyrrolidone (PVP) were investigated as carrier polymers for preparing and stabilizing cryogenic co-ground SDs of poorly water-soluble piroxicam (PRX). CPSC was isolated from pine wood (Pinus sylvestris). Raman and Fourier transform infrared (FTIR) spectroscopy, X-ray powder diffraction (XRPD) and differential scanning calorimetry (DSC) were used for characterizing the solid-state changes and drug-polymer interactions. High-resolution scanning electron microscope (SEM) was used to analyze the particle size and surface morphology of starting materials and final cryogenic co-ground SDs. In addition, the molecular aspects of drug-polymer interactions and stabilization mechanisms are presented. The results showed that the carrier polymer influenced both the degree of amorphization of PRX and stabilization against crystallization. The cryogenic co-ground SDs prepared from PVP showed an enhanced dissolution rate of PRX, while the corresponding SDs prepared from CPSC exhibited a clear sustained release behavior. In conclusion, cryogenic co-grinding provides a versatile method for preparing amorphous SDs of poorly water-soluble APIs. The solid-state stability and dissolution behavior of such co-ground SDs are to a great extent dependent on the carrier polymer used.

  14. Study of optical and electrical properties of water-soluble conjugated poly(3-hexylthiophene) on different grain-sized mesoporous TiO{sub 2} layers

    Energy Technology Data Exchange (ETDEWEB)

    Thalluri, Gopala Krishna V.V.; Bolsée, Jean-Christophe; Madapati, Saipriya [Institute for Materials Research (IMO), Hasselt University, Wetenschapspark 1, BE-3590 Diepenbeek (Belgium); Vanderzande, Dirk [Institute for Materials Research (IMO), Hasselt University, Wetenschapspark 1, BE-3590 Diepenbeek (Belgium); IMEC vzw, Division IMOMEC, Wetenschapspark 1, BE-3590 Diepenbeek (Belgium); Manca, Jean V., E-mail: jean.manca@uhasselt.be [Institute for Materials Research (IMO), Hasselt University, Wetenschapspark 1, BE-3590 Diepenbeek (Belgium); IMEC vzw, Division IMOMEC, Wetenschapspark 1, BE-3590 Diepenbeek (Belgium)

    2014-04-01

    Solid-state hybrid solar cells are promising candidates for future low-cost photovoltaic energy generation that are based on polymer/metal oxide donor/acceptor heterojunctions. However, a critical drawback of hybrid solar cells is the usage of toxic and environmental unfriendly organic solvents in the phase of preparation. In terms of environmental impact, “green” and safer materials are required towards processing of eco-friendly hybrid solar cells. In this work, during processing phase of eco-friendly hybrid solar cells, aqueous-soluble conjugated poly(3-hexylthiophene) material is used as photo-active and hole transporting layer and TiO{sub 2} layer as electron accepting layer. Optical, topographical and morphological characterizations on different grain-sized TiO{sub 2} layers with polymer films are studied. The influence of eco-friendly hybrid solar cell electrical properties in combination with different grain-sized TiO{sub 2} layers measured under N{sub 2} and ambient conditions are discussed. It is important to understand these properties for further optimizations. - Highlights: • Morphological properties of different grain-sized TiO{sub 2} layers. • Optical properties with and without water-soluble poly(3-hexylthiophene) on TiO{sub 2} layers. • Electrical measurements. • Eco-friendly hybrid solar cells.

  15. Conjugated Polymer Nanoparticles for Bioimaging

    Directory of Open Access Journals (Sweden)

    Yasmine Braeken

    2017-12-01

    Full Text Available During the last decade, conjugated polymers have emerged as an interesting class of fluorescence imaging probes since they generally show high fluorescence brightness, high photostability, fast emission rates, non-blinking behavior and low cytotoxicity. The main concern related to most conjugated polymers is their lack of hydrophilicity and thereby poor bio-availability. This can, however, be overcome by the formulation of conjugated polymer nanoparticles in aqueous medium. This review provides an overview of the different techniques employed for the preparation of conjugated polymer nanoparticles, together with methods to improve their photoluminescence quantum yields. For selective targeting of specific cells, dedicated surface functionalization protocols have been developed, using different functional groups for ligand immobilization. Finally, conjugated polymer nanoparticles have recently also been employed for theranostic applications, wherein the particles are simultaneously used as fluorescent probes and carriers for anti-tumor drugs.

  16. 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.

  17. Evaluation of chitosan–anionic polymers based tablets for extended-release of highly water-soluble drugs

    Directory of Open Access Journals (Sweden)

    Yang Shao

    2015-02-01

    Full Text Available The objective of this study is to develop chitosan–anionic polymers based extended-release tablets and test the feasibility of using this system for the sustained release of highly water-soluble drugs with high drug loading. Here, the combination of sodium valproate (VPS and valproic acid (VPA were chosen as the model drugs. Anionic polymers studied include xanthan gum (XG, carrageenan (CG, sodium carboxymethyl cellulose (CMC-Na and sodium alginate (SA. The tablets were prepared by wet granulation method. In vitro drug release was carried out under simulated gastrointestinal condition. Drug release mechanism was studied. Compared with single polymers, chitosan–anionic polymers based system caused a further slowdown of drug release rate. Among them, CS–xanthan gum matrix system exhibited the best extended-release behavior and could extend drug release for up to 24 h. Differential scanning calorimetry (DSC and Fourier transform infrared spectroscopy (FTIR studies demonstrated that polyelectrolyte complexes (PECs were formed on the tablet surface, which played an important role on retarding erosion and swelling of the matrix in the later stage. In conclusion, this study demonstrated that it is possible to develop highly water-soluble drugs loaded extended-release tablets using chitosan–anionic polymers based system.

  18. Biphasic and SAPC Hydroformylation Catalyzed by Rh-phosphines Bound to Water-Soluble Polymers

    DEFF Research Database (Denmark)

    Malmstrøm, Torsten; Andersson, Carlaxel; Hjortkjær, Jes

    1999-01-01

    Coupling of the triphenylphosphine moiety to poly-acrylic acid and poly-ethyleneimine respectively afford the macromolecular ligands PAA-PNH and PEI-PNH. Reaction of the ligands with Rh(CO)2(acac) give water-soluble complexes that are active as catalysts in the hydroformylation ofdifferent olefin...... PEI-PNH as ligands show lower stability and activity in both SAPC and biphasic applications....

  19. Reversible Thermoassociation of Water-Soluble Polymers Thermoassociation réversible de polymères hydrosolubles

    Directory of Open Access Journals (Sweden)

    L'alloret F.

    2006-12-01

    Full Text Available In various industrial fields, water soluble polymers are commonly used as thickening agents to control the reology of aqueous fluids. Nevertheless, their properties are weakened as the temperature increases. In order to overcome this problem, the concept of thermoassociativewater soluble polymers was developed. Such new amphilic systems can be obtained by grafting on an hydrophilic backbone, side chains which become non water soluble above a Lower Critical Solution Temperature (LCST. Semidilute solutions of these copolymers present reversible thickening properties as the temperature increases and reaches a critical value, close to the side chains LCST. This behaviour can be related to the agregation of the grafts above their LCST, into hydrophobic microdomains , inducing the formation of a three dimensional network. At higher temperature, the viscosity of the solution sheared at a constant rate reaches a maximum value. This can be interpreted in terms of the reorganisation of the physical network under shear, from a structure with mainly intermolecular associationsto a system with an increasing number of intramolecular associations . Owing to the diversity of water soluble polymers exhibiting a phase separation on heating (LCST, different thermoassociativecopolymers were realized [1] and [2], using either polyelectrolyte or neutral hydrophilic backbone. In the aim of applications of such systems in the oilfield industry, copolymers containing 2-acrylamido 2-methyl propane sulfonic acid (AMPS were developed, using polyethylene oxide (PEO as LCST grafts. A general description of their rheological behaviour will be given here. Their properties can be controlled either by varying the solution characteristic (polymer concentration, salinity, etc. or by modifying the chemical structure of the copolymer (grafting ratio, molecular weight of the backbone, etc. . This rheological study showed the potentiality of the thermoassociativesystem, particularly

  20. Effect of surfactants or a water soluble polymer on the crystal transition of clarithromycin during a wet granulation process.

    Science.gov (United States)

    Nozawa, Kenji; Iwao, Yasunori; Noguchi, Shuji; Itai, Shigeru

    2015-11-10

    To generate products containing a stable form of clarithromycin (CAM) (form II) regardless of the initial crystal form of CAM or type of granulation solvent, the effects of five surfactants, or a water-soluble polymer (macrogol 400) were determined on the crystal transition of CAM. The metastable form (form I) was kneaded with water, after adding surfactants, or a water-soluble polymer. Form II was also kneaded with ethanol, after adding the same additives. The resulting samples were analyzed by powder X-ray diffraction. Form I was completely converted to form II by a wet granulation using water with additives bearing polyoxyethylene chains such as polysorbate 80 (PS80), polyoxyl 40 stearate or macrogol 400. The granulation of the form II using ethanol with these additives did not result in a crystal transition to form I. Furthermore, CAM tablets were manufactured using granules with PS80, and these crystal forms and dissolution behaviors were investigated. As a result, the wet granulation of CAM with PS80 gave CAM tablets containing only form II and PS80 did not have any adverse effects on tablet characteristics. Therefore, these data suggests that the crystal form of CAM can be controlled to be form II using a wet granulation process with additives bearing polyoxyethylene chains regardless of the initial crystal form of CAM or type of granulation solvent. Copyright © 2015 Elsevier B.V. All rights reserved.

  1. Water-Soluble Polymers with Strong Photoluminescence through an Eco-Friendly and Low-Cost Route.

    Science.gov (United States)

    Guo, Zhaoyan; Ru, Yue; Song, Wenbo; Liu, Zhenjie; Zhang, Xiaohong; Qiao, Jinliang

    2017-07-01

    Photoluminescence (PL) of nonconjugated polymers brings a favorable opportunity for low-cost and nontoxic luminescent materials, while most of them still exhibit relatively weak emission. Strong PL from poly[(maleic anhydride)-alt-(vinyl acetate)] (PMV) from low-cost monomer has been found in organic solvents, yet the necessity of noxious solvents would hinder its practical applications. Herein, through a novel, eco-friendly, and one-step route, PMV-derived PL polymers can be fabricated with the highest quantum yield of 87% among water-soluble nonconjugated PL polymers ever reported. These PMV-derived polymers emit strong blue emission in both solutions and solids, and can be transformed into red-emission agents easily. These PL polymers exhibit application potentials in light-conversion agricultural films. It is assumed that this work not only puts forward a convenient preparation routine for nonconjugated polymers with high PL, but also provides an industrial application possibility for them. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. 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...... for scalable PSCs fully printed under ambient conditions [Adv. Energy Mater. 2015, 5, 1402186]. PPDTBT resulted to be the conjugated polymer with the best photovoltaic performance within the 104 synthesized macromolecules. Therefore, further studies have been done on such material. The impact of side chain...... arylation (DAr) and direct arylation polymerization (DArP) have been applied to the preparation of PPDTBT, making this polymer readily available in only 4 synthetic steps and thus easily transferable to a large scale-production setup. DArP avoids organometallic species and therefore is an appealing...

  3. Influence of water-soluble polymers on the in vitro performance of floating mucoadhesive tablets containing metformin.

    Science.gov (United States)

    Rajab, Mazen; Jouma, Muhidien; Neubert, Reinhard H H; Dittgen, Michael

    2014-07-01

    The in vitro performance of floating mucoadhesive metformin tablets was optimized using different polymer ratios of polyvinylpyrrolidone (PVP) tamarind seed gum (TSG) and hydroxypropylmethylcellulose (HPMC). The objectives of this investigation were to investigate the combinatorial effects of PVP, TSG and HPMC; to study the work of adhesion measured on stainless steel (Wss) and on rabbit gastric mucosa (Wgm); and a comparison of hydrophilic and more hydrophobic tablets. In vitro performance was measured as tablet hardness (H), tablet floating lag time (FLT), time needed to release 60% of drug content (t60%), swelling thickness (S), Wss and Wgm. To compare the effects, a simplex lattice mixture design was used. H, FLT, Wss and Wgm were found dependent on polymer ratio. H was increased when PVP ratio was increased. FLT, Wss and Wgm were increased when HPMC ratio was increased. The p value for the lack of fit for all models were greater than 0.05. An approximate linear correlation between Wgm and Wss was established (R(2) = 0.71). The tablets containing PVP resulted in larger H, shorter FLT and t60%, whereas Wss and Wgm were enhanced. The different in vitro performance of tablets containing different water-soluble polymers could be explained partially by the differences in the hydrophilic properties of the polymers and the ability of PVP to interact with HPMC or TSG. An equation established is used to conclude mucoadhesion based on adhesion measurements on stainless steel.

  4. 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 fluorination.

  5. Enhanced photophysics of conjugated polymers

    Energy Technology Data Exchange (ETDEWEB)

    Chen, Liaohai [Darien, IL

    2007-06-12

    A particulate fluorescent conjugated polymer surfactant complex and method of making and using same. The particles are between about 15 and about 50 nm and when formed from a lipsome surfactant have a charge density similar to DNA and are strongly absorbed by cancer cells.

  6. Enhanced encapsulation and bioavailability of breviscapine in PLGA microparticles by nanocrystal and water-soluble polymer template techniques.

    Science.gov (United States)

    Wang, Hong; Zhang, Guangxing; Ma, Xueqin; Liu, Yanhua; Feng, Jun; Park, Kinam; Wang, Wenping

    2017-06-01

    Poly (lactide-co-glycolide) (PLGA) microparticles are widely used for controlled drug delivery. Emulsion methods have been commonly used for preparation of PLGA microparticles, but they usually result in low loading capacity, especially for drugs with poor solubility in organic solvents. In the present study, the nanocrystal technology and a water-soluble polymer template method were used to fabricate nanocrystal-loaded microparticles with improved drug loading and encapsulation efficiency for prolonged delivery of breviscapine. Breviscapine nanocrystals were prepared using a precipitation-ultrasonication method and further loaded into PLGA microparticles by casting in a mold from a water-soluble polymer. The obtained disc-like particles were then characterized and compared with the spherical particles prepared by an emulsion-solvent evaporation method. X-ray powder diffraction (XRPD) and confocal laser scanning microscopy (CLSM) analysis confirmed a highly-dispersed state of breviscapine inside the microparticles. The drug form, loading percentage and fabrication techniques significantly affected the loading capacity and efficiency of breviscapine in PLGA microparticles, and their release performance as well. Drug loading was increased from 2.4% up to 15.3% when both nanocrystal and template methods were applied, and encapsulation efficiency increased from 48.5% to 91.9%. But loading efficiency was reduced as the drug loading was increased. All microparticles showed an initial burst release, and then a slow release period of 28days followed by an erosion-accelerated release phase, which provides a sustained delivery of breviscapine over a month. A relatively stable serum drug level for more than 30days was observed after intramuscular injection of microparticles in rats. Therefore, PLGA microparticles loaded with nanocrystals of poorly soluble drugs provided a promising approach for long-term therapeutic products characterized with preferable in vitro and in vivo

  7. Superhydrophilic molecularly imprinted polymers based on a water-soluble functional monomer for the recognition of gastrodin in water media.

    Science.gov (United States)

    Ji, Wenhua; Zhang, Mingming; Wang, Daijie; Wang, Xiao; Liu, Jianhua; Huang, Luqi

    2015-12-18

    In this study, the first successfully developed superhydrophilic molecularly imprinted polymers (MIPs) for gastrodin recognition have been described. MIPs were prepared via the bulk polymerization process in an aqueous solution using alkenyl glycosides glucose (AGG) as the water-soluble functional monomer. The non-imprinted polymers (NIPs) were also synthesized using the same method without the use of the template. The dynamic water contact angles and photographs of the dispersion properties confirmed that the molecularly imprinted polymers displayed excellent superhydrophilicity. The results demonstrated that the MIPs exhibited high selectivity and an excellent imprinting effect. A molecularly imprinted solid phase extraction (MISPE) method was established. Optimization of various parameters affecting MISPE was investigated. Under the optimized conditions, a wide linear range (0.001-100.0μgmL(-1)) and low limits of detection (LOD) and quantification (LOQ) (0.03 and 0.09ngmL(-1), respectively) were achieved. When compared with the NIPs, higher recoveries (90.5% to 97.6%) of gastrodin with lower relative standard deviations values (below 6.4%) using high performance liquid chromatography were obtained at three spiked levels in three blank samples. These results demonstrated one efficient, highly selective and environmentally-friendly MISPE technique with excellent reproducibility for the purification and pre-concentration of gastrodin from an aqueous extract of Gastrodia elata roots. Copyright © 2015 Elsevier B.V. All rights reserved.

  8. Dilute and Semidilute Solutions of a Nonionic, Rigid, Water-soluble Polymer

    Science.gov (United States)

    Russo, Paul; Huberty, Wayne; Zhang, Donghui; Water-Soluble Rodlike Polymer Team Collaboration

    2014-03-01

    The solution physics of random polymer chains was established largely on the behavior of commercial polymers such as polystyrene for organic solvents or nonionic poly(ethyleneoxide) for aqueous solvents. Not only are these materials widely available for industrial use, they can be synthesized to be essentially monodisperse. When it comes to stiff polymers, good choices are few and less prone to be used in industrial applications. Much was learned from polypeptides such as poly(benzylglutamate) or poly(stearylglutamate) in polar organic solvents and nonpolar organic solvents, respectively, but aqueous systems generally require charge. Poly(Nɛ-2-[2-(2-Methoxyethoxy) ethoxy]acetyl-L-Lysine) a.k.a. PEGL was pioneered by Deming and coworkers. In principle, PEGL provides a convenient platform from which to study stiff polymer behavior--phase relations, dynamics, liquid crystal formation and gelation--all with good molecular weight control and uniformity and without electrical charge. Still, a large gap in knowledge exists between PEGL and traditional rodlike polymer systems. To narrow this gap, dynamic and static scattering, circular dichroism, and viscosity measurements have been made in dilute and semidilute solutions as necessary preliminaries for lyotropic liquid crystalline and gel phases. Supported by NSF DMR 1306262. Department of Chemistry and Macromolecular Studies Group. Current address: Georgia Institute of Technology, School of Materials Science and Engineering.

  9. Synthesis and Evaluation of a Water-Soluble Hyperbranched Polymer as Enhanced Oil Recovery Chemical

    Directory of Open Access Journals (Sweden)

    Nanjun Lai

    2013-01-01

    Full Text Available A novel hyperbranched polymer was synthesized using acrylamide (AM, acrylic acid (AA, N-vinyl-2-pyrrolidone (NVP, and dendrite functional monomer as raw materials by redox initiation system in an aqueous medium. The hyperbranched polymer was characterized by infrared (IR spectroscopy, 1H NMR spectroscopy, 13C NMR spectroscopy, elemental analysis, and scanning electron microscope (SEM. The viscosity retention rate of the hyperbranched polymer was 22.89% higher than that of the AM/AA copolymer (HPAM at 95°C, and the viscosity retention rate was 8.17%, 12.49%, and 13.68% higher than that of HPAM in 18000 mg/L NaCl, 1800 mg/L CaCl2, and 1800 mg/L MgCl2·6H2O brine, respectively. The hyperbranched polymer exhibited higher apparent viscosity (25.2 mPa·s versus 8.1 mPa·s under 500 s−1 shear rate at 80°C. Furthermore, the enhanced oil recovery (EOR of 1500 mg/L hyperbranched polymer solutions was up to 23.51% by the core flooding test at 80°C.

  10. Hyphenation of aqueous liquid chromatography to pyrolysis-gas chromatography and mass spectrometry for the comprehensive characterization of water-soluble polymers

    NARCIS (Netherlands)

    Kaal, E.R.; Kurano, M.; Geissler, M.; Janssen, H.-G.

    2008-01-01

    A recently developed hyphenated system for "organic" size-exclusion chromatography-pyrolysis-gas chromatography-mass spectrometry (SEC-Py-GC-MS) is adapted to allow the use of aqueous LC eluents as applied in the characterization of water-soluble polymers. The system uses syringe-based transfer of

  11. Photoluminescence of Conjugated Star Polymers

    Science.gov (United States)

    Ferguson, J. B.; Prigodin, N. V.; Epstein, A. J.; Wang, F.

    2000-10-01

    Higher dimensionality "star" polymers provide new properties beyond those found in their linear analogs. They have been used to improving electronic properties for nonlinear optics through exciton transfer and molecular antenna structures for example (M. Kawa, J. M. J. Frechet, Chem. Mater. 10, 286 (1998).). We report on photoluminescence properties of star polymers with a hyperbranched core (both hyperbranched phenlyene and hyperbranched triphenylamine) and polyhexylthiophene arms. The arm is a conjugated oligomer of polythiophene that has been investigated extensively for metallic like conductivity when doped as well as utilized in field effect transistors in its undoped form (A. Tsumara, H. Koezuka, T. Ando, Appl. Phys. Lett. 49, 1210 (1986).). The cores are respectively, a nonconjugated polymer in the case of hyperbranched phenlyene and a conjugated polymer in the case of hyperbranched triphenylamine. The photoluminesce spectrum (λ_max at 575 nm) is identical for both star polymers with the two electronically different hyperbranched cores and for linear polythiophene alone. We conclude the wave functions of the core and arms do not strongly interact to form states different from their individual states and excitons formed on the hyperbranched cores migrate to the lower bandgap polythiophene before recombining.

  12. Chromo- and fluorophoric water-soluble polymers and silica particles by nucleophilic substitution reaction of poly(vinyl amine

    Directory of Open Access Journals (Sweden)

    Katja Hofmann

    2010-07-01

    Full Text Available Novel chromophoric and fluorescent carbonitrile-functionalized poly(vinyl amine (PVAm and PVAm/silica particles were synthesized by means of nucleophilic aromatic substitution of 8-oxo-8H-acenaphtho[1,2-b]pyrrol-9-carbonitrile (1 with PVAm in water. The water solubility of 1 has been mediated by 2,6-O-β-dimethylcyclodextrin or by pre-adsorption onto silica particles. Furthermore, 1 was converted with isopropylamine into the model compound 1-M. All new compounds were characterized by NMR, FTIR, UV–vis and fluorescence spectroscopy. The solvent-dependent UV–vis absorption and fluorescence emission band positions of the model compound and the carbonitrile-functionalized PVAm were studied and interpreted using the empirical Kamlet–Taft solvent parameters π* (dipolarity/polarizability, α (hydrogen-bond donating capacity and β (hydrogen-accepting ability in terms of the linear solvation energy relationship (LSER. The solvent-independent regression coefficients a, b and s were determined using multiple linear correlation analysis. It is shown, that the chains of the polymer have a significant influence on the solvatochromic behavior of 1-P. The structure of the carbonitrile 1-Si bound to polymer-modified silica particles was studied by means of X-ray photoelectron spectroscopy (XPS and Brunauer–Emmett–Teller (BET measurements. Fluorescent silica particles were obtained as shown by fluorescence spectroscopy with a diffuse reflectance technique.

  13. Development of Lipid-Shell and Polymer Core Nanoparticles with Water-Soluble Salidroside for Anti-Cancer Therapy

    Directory of Open Access Journals (Sweden)

    Dai-Long Fang

    2014-02-01

    Full Text Available Salidroside (Sal is a potent antitumor drug with high water-solubility. The clinic application of Sal in cancer therapy has been significantly restricted by poor oral absorption and low tumor cell uptake. To solve this problem, lipid-shell and polymer-core nanoparticles (Sal-LPNPs loaded with Sal were developed by a double emulsification method. The processing parameters including the polymer types, organic phase, PVA types and amount were systemically investigated. The obtained optimal Sal-LPNPs, composed of PLGA-PEG-PLGA triblock copolymers and lipids, had high entrapment efficiency (65%, submicron size (150 nm and negatively charged surface (−23 mV. DSC analysis demonstrated the successful encapsulation of Sal into LPNPs. The core-shell structure of Sal-LPNPs was verified by TEM. Sal released slowly from the LPNPs without apparent burst release. MTT assay revealed that 4T1 and PANC-1 cancer cell lines were sensitive to Sal treatment. Sal-LPNPs had significantly higher antitumor activities than free Sal in 4T1 and PANC-1 cells. The data indicate that LPNPs are a promising Sal vehicle for anti-cancer therapy and worthy of further investigation.

  14. Development of Lipid-Shell and Polymer Core Nanoparticles with Water-Soluble Salidroside for Anti-Cancer Therapy

    Science.gov (United States)

    Fang, Dai-Long; Chen, Yan; Xu, Bei; Ren, Ke; He, Zhi-Yao; He, Li-Li; Lei, Yi; Fan, Chun-Mei; Song, Xiang-Rong

    2014-01-01

    Salidroside (Sal) is a potent antitumor drug with high water-solubility. The clinic application of Sal in cancer therapy has been significantly restricted by poor oral absorption and low tumor cell uptake. To solve this problem, lipid-shell and polymer-core nanoparticles (Sal-LPNPs) loaded with Sal were developed by a double emulsification method. The processing parameters including the polymer types, organic phase, PVA types and amount were systemically investigated. The obtained optimal Sal-LPNPs, composed of PLGA-PEG-PLGA triblock copolymers and lipids, had high entrapment efficiency (65%), submicron size (150 nm) and negatively charged surface (−23 mV). DSC analysis demonstrated the successful encapsulation of Sal into LPNPs. The core-shell structure of Sal-LPNPs was verified by TEM. Sal released slowly from the LPNPs without apparent burst release. MTT assay revealed that 4T1 and PANC-1 cancer cell lines were sensitive to Sal treatment. Sal-LPNPs had significantly higher antitumor activities than free Sal in 4T1 and PANC-1 cells. The data indicate that LPNPs are a promising Sal vehicle for anti-cancer therapy and worthy of further investigation. PMID:24573250

  15. Photoconductive properties of conjugated polymers

    CERN Document Server

    Halls, J J M

    1997-01-01

    The research described in my dissertation has involved the fabrication and characterisation of photovoltaic cells based on conjugated polymers, including the widely studied polymer poly(p-phenylenevinylene). These materials have semiconducting properties which arise from the delocalisation of electrons along the pi-electron systems of the polymer chains. Research into these materials is motivated both by their novel electronic properties, and also their potential for use in a wide range of applications including light-emitting diodes (LEDs), thin-film transistors, and photovoltaic cells (solar cells and light detectors). Light absorbed in a photovoltaic cell generates opposite charges which are collected at two different electrodes, giving rise to an electric current

  16. A New Water-Soluble Nanomicelle Formed through Self-Assembly of Pectin-Curcumin Conjugates: Preparation, Characterization, and Anticancer Activity Evaluation.

    Science.gov (United States)

    Bai, Feng; Diao, Jiajing; Wang, Ying; Sun, Shixin; Zhang, Hongmei; Liu, Yunyun; Wang, Yanqing; Cao, Jian

    2017-08-16

    Curcumin is a dominating active component of Curcuma longa and has been studied widely because of its prominent biological activities. The extremely low aqueous solubility, stability, and bioavailability of curcumin limit its application in the field of medicine. In this study, we developed pectin-curcumin (PEC-CCM) conjugates that could self-assemble water-soluble nanomicelles in aqueous solution. The structure of PEC-CCM conjugates was characterized by ultraviolet-visible spectra, fluorescence spectra, Fourier transform infrared spectroscopy, and (1)H nuclear magnetic resonance spectroscopy. The thermal property of PEC-CCM conjugates was investigated by thermogravimetric analysis. It was found that PEC-CCM conjugates had formed nanomicelles in aqueous medium via self-assembly. These nanomicelles were observed as small spheres or ellipsoids and aggregated with a size range of 70-190 nm by transmission electron microscopy analysis. In a solution of nanomicelles, the stability of curcumin was improved, and its antioxidant property was preserved. The anticancer activity of PEC-CCM conjugates was quantified by the MTT [3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide] assay using a hepatic cancer cell line (HepG2), a breast cancer cell line (MCF-7), a cervical cancer cell line (HeLa), and a human normal kidney cell line (293A). It was found that the curcumin of PEC-CCM conjugates had a more significant inhibitory effect on cancer cells and was less cytotoxic to normal cells than free curcumin was. PEC-CCM conjugates have great potential for some food and pharmaceutical applications.

  17. Electrospun water soluble polymer mat for ultrafast release of Donepezil HCl

    Directory of Open Access Journals (Sweden)

    2010-12-01

    Full Text Available Electrostatic spinning (Electrospinning, ES was applied to prepare Donepezil HCl loaded nanofibers as a potential orally dissolving dosage form. Electrospinning of water solutions of different polymers were performed in order to fabricate a consistent and removable web on the collector with ultra-fast dissolution in water based media. Poly(vinyl-alcohol of low molecular weight was found to be the most appropriate for this purpose. Morphology of the prepared nanofibers was characterized by scanning electron microscope as a function of viscosity and drug content. Diameters of the fibers were between 100 and 300 nm with narrow distribution. In vitro drug release of the webs was immediate (less than 30 s after immersion independently of their drug content owing to the formed huge surface area, while cast films with the same compositions and commercial tablets needed 30 min or more for complete dissolution. The developed technology for the preparation of orally dissolving web (ODW formulations is a promising way for producing effective and acceptable dosage forms for children, older people and patients with dysphagia.

  18. Preparation and sonodynamic activities of water-soluble tetra-α-(3-carboxyphenoxyl) zinc(II) phthalocyanine and its bovine serum albumin conjugate.

    Science.gov (United States)

    Xu, He-Nan; Chen, Hai-Jun; Zheng, Bi-Yuan; Zheng, Yun-Quan; Ke, Mei-Rong; Huang, Jian-Dong

    2015-01-01

    Sonodynamic therapy (SDT) is a new approach for cancer treatment, involving the synergistic effect of ultrasound and certain chemical compounds termed as sonosensitizers. A water-soluble phthalocyanine, namely tetra-α-(3-carboxyphenoxyl) zinc(II) phthalocyanine (ZnPcC4), has been prepared and characterized. The interactions between ZnPcC4 and bovine serum albumin (BSA) were also investigated by absorption and fluorescence spectroscopy. It was found that there were strong interactions between ZnPcC4 and BSA with a binding constant of 6.83×10(7)M(-1). A non-covalent BSA conjugate of ZnPcC4 (ZnPcC4-BSA) was prepared. Both ZnPcC4 and ZnPcC4-BSA exhibited efficient sonodynamic activities against HepG2 human hepatocarcinoma cells. Compared with ZnPcC4, conjugate ZnPcC4-BSA showed a higher sonodynamic activity with an IC50 value of 7.5μM. Upon illumination with ultrasound, ZnPcC4-BSA can induce an increase of intracellular reactive oxygen species (ROS) level, resulting in cellular apoptosis. The results suggest that the albumin conjugates of zinc(II) phthalocyanines functionalized with carboxyls can serve as promising sonosensitizers for sonodynamic therapy. Copyright © 2014 Elsevier B.V. All rights reserved.

  19. Evaluation of Hydrate Inhibition Performance of Water-soluble Polymers using Torque Measurement and Differential Scanning Calorimeter

    Energy Technology Data Exchange (ETDEWEB)

    Shin, Kyuchul; Park, Juwoon; Kim, Jakyung; Kim, Hyunho; Seo, Yutaek [KAIST, Daejeon (Korea, Republic of); Lee, Yohan; Seo, Yongwon [UNIST, Ulsan (Korea, Republic of)

    2014-12-15

    In this work, hydrate inhibition performance of water-soluble polymers including pyrrolidone, caprolactam, acrylamide types were evaluated using torque measurement and high pressure differential scanning calorimeter (HP µ-DSC). The obtained experimental results suggest that the studied polymers represent the kinetic hydrate inhibition (KHI) performance. 0.5 wt% polyvinylcaprolactam (PVCap) solution shows the hydrate onset time of 34.4 min and subcooling temperature of 15.9 K, which is better KHI performance than that of pure water - hydrate onset time of 12.3 min and subcooling temperature of 6.0 K. 0.5 wt% polyvinylpyrrolidone (PVP) solution shows the hydrate onset time of 27.6 min and the subcooling temperature of 13.2 K while polyacrylamide-co-acrylic acid partial sodium salt (PAM-co-AA) solution shows less KHI performance than PVP solution at both 0.5 and 5.0 wt%. However, PAM-co-AA solution shows slow growth rate and low hydrate amount than PVCap. In addition to hydrate onset and growth condition, torque change with time was investigated as one of KHI evaluation methods. 0.5 wt% PVCap solution shows the lowest average torque of 6.4 N cm and 0.5 wt% PAM-co-AA solution shows the average torque of 7.2 N cm. For 0.5 wt% PVP solution, it increases 11.5 N cm and 5.0 wt% PAM-co-AA solution shows the maximum average torque of 13.4 N cm, which is similar to the average torque of pure water, 15.2 N cm. Judging from the experimental results obtained by both an autoclave and a HP µ-DSC, the PVCap solution shows the best performance among the KHIs in terms of delaying hydrate nucleation. From these results, it can be concluded that the torque change with time is useful to identify the flow ability of tested solution, and the further research on the inhibition of hydrate formation can be approached in various aspects using a HP µ-DSC.

  20. Polymer-peptide conjugates for angiogenesis targeted tumor radiotherapy

    Energy Technology Data Exchange (ETDEWEB)

    Mitra, Amitava [Department of Pharmaceutical Sciences, University of Maryland, Baltimore, MD 21201 (United States); Center for Nanomedicine and Cellular Delivery, University of Maryland, Baltimore, MD 21201 (United States); Nan, Anjan [Department of Pharmaceutical Sciences, University of Maryland, Baltimore, MD 21201 (United States); Center for Nanomedicine and Cellular Delivery, University of Maryland, Baltimore, MD 21201 (United States); Papadimitriou, John C. [Department of Pathology, University of Maryland, Baltimore, MD 21201 (United States); Ghandehari, Hamidreza [Department of Pharmaceutical Sciences, University of Maryland, Baltimore, MD 21201 (United States) and Center for Nanomedicine and Cellular Delivery, University of Maryland, Baltimore, MD 21201 (United States) and Greenebaum Cancer Center, University of Maryland, Baltimore, MD 21201 (United States)]. E-mail: hghandeh@rx.umaryland.edus; Line, Bruce R. [Center for Nanomedicine and Cellular Delivery, University of Maryland, Baltimore, MD 21201 (United States) and Greenebaum Cancer Center, University of Maryland, Baltimore, MD 21201 (United States) and Division of Nuclear Medicine, Department of Radiology, University of Maryland, Baltimore, MD 21201 (United States)]. E-mail: bline@umm.edu

    2006-01-15

    Introduction: New methods of delivering radiotherapy to sites of occult or disseminated cancer are needed to control the disease and address the failure of conventional therapy. Because tumor cells rely on angiogenesis for survival, we assessed the effectiveness of {beta}-emitter radiotherapy delivered by polymer-peptide conjugates that target tumor neovasculature. This molecularly targeted radiation is intended to damage both the endothelial bed and surrounding neoplastic cells. Methods: N-(2-Hydroxypropyl) methacrylamide (HPMA), a biocompatible and water-soluble copolymer, was derivatized to incorporate side chains for {sup 99m}Tc and {sup 9}Y chelation and was further conjugated to a {alpha}{sub V}{beta}{sub 3} integrin-targeting peptide (RGD4C). The HPMA copolymer-RGD4C conjugate was characterized by its side-chain contents, in vitro endothelial cell adhesion assay and its biodistribution and antitumor effectiveness in a SCID mouse xenograft model of human prostate carcinoma. Results: The conjugate contained about 16 RGD4C moieties per polymer backbone. Tumor accumulation significantly increased (P<.01) over time from 1.05{+-}0.03 % injected dose (%ID)/g tissue at 1 h to 4.32{+-}0.32% at 72 h. The activity in major normal tissues significantly decreased (P<.05) during that period. At 21 days, the control tumors increased 442% in volume from baseline. In contrast, a 7% and a 63% decrease of tumor volume were observed for the 100- and 250-{mu}Ci {sup 9}Y treatment groups, respectively. Histopathological examination revealed increased apoptosis in the treated tumors with no acute signs of radiation-induced toxicity to other organs. Conclusion: This copolymer-peptide conjugate targets tumor angiogenic vessels and delivers sufficient radiotherapy to arrest tumor growth.

  1. Application of hydrophobically modified water-soluble polymers for the dispersion of hydrophobic magnetic nanoparticles in aqueous media.

    Science.gov (United States)

    Iatridi, Zacharoula; Georgiadou, Violetta; Menelaou, Melita; Dendrinou-Samara, Catherine; Bokias, Georgios

    2014-06-21

    Hydrophobically modified water-soluble polymers (HMWSPs), comprised of a poly(sodium methacrylate) (PMANa) or poly(sodium acrylate) (PANa) backbone and pendent dodecyl methacrylate (DMA) or dodecyl acrylamide (DAAm) chains, respectively, were synthesized. The hydrophobic content of the copolymers, P(MANa-co-DMA) and P(ANa-co-DAAm), is in the range of 0 to 25 mol%, while their weight-average molar mass varies from ~10 000 up to ~75 000. Their self-assembly behavior in dilute aqueous solution was followed through Nile Red probing, DLS and TEM measurements. The critical micelle concentration (CMC) is mainly controlled by the hydrophobic content and not the molar mass of the copolymers. Above CMC, spherical and large-compound micelles are identified by DLS and TEM. Moreover, oleylamine coated CoFe2O4 nanoparticles (CoFe2O4@OAm MNPs) of 9.4 nm with a saturation magnetization Ms = 85 emu g(-1) were solvothermally prepared. The hydrophobic CoFe2O4@OAm MNPs were successfully encapsulated into the hydrophobic cores of the structures formed by the copolymers above CMC through a solvent mixing procedure, and in that way hydrophilic CoFe2O4@HMWSP nanohybrids resulted. For comparison purposes, two alternate phase transfer approaches were also used to convert CoFe2O4@OAm MNPs to hydrophilic ones: (a) addition of a coating layer by cetyltrimethyl ammonium bromide (CTAB) and (b) by the ligand exchange procedure with 2,3-dimercaptosuccinic acid (DMSA). NMR transverse relaxivity measurements of the aqueous suspensions of CoFe2O4@P(ANa-co-DAAm), CoFe2O4@CTAB and CoFe2O4@DMSA were recorded and the r2 relaxivity was determined. CoFe2O4@CTAB demonstrated the highest r2 relaxivity of 554.0 mM(-1) s(-1), while CoFe2O4@P(ANa-co-DAAm) and CoFe2O4@DMSA showed lower values of 313.6 mM(-1) s(-1) and 76.3 mM(-1) s(-1), respectively.

  2. Solventless processing of conjugated polymers - a review

    OpenAIRE

    Brandão, Lúcia; Viana, Júlio; Bucknall, David G.; Bernardo, Gabriel

    2014-01-01

    The molecular mobility of polymers in their solid or molten states allows their processing without the need for toxic, “non-friendly” solvents. In this work, the main features of solvent-free processing methods applied to conjugated polymers are reviewed taking into consideration that these materials are largely used in a broad range of (opto-)electronic applications, including organic field-effect transistors, polymer light-emitting diodes and polymer photovoltaic devices. This review addres...

  3. A water-soluble inclusion complex of pedunculoside with the polymer β-cyclodextrin: a novel anti-inflammation agent with low toxicity.

    Directory of Open Access Journals (Sweden)

    Chang Liu

    Full Text Available More than 50% of new drug candidates in drug discovery are lipophilic and exhibit poor aqueous solubility, which results in poor bioavailability and a lack of dose proportionality. Here, we improved the solubility of pedunculoside (PE by generating a water-soluble inclusion complex composed of PE and the polymer β-cyclodextrin (CDP. We characterized this novel complex by 1H NMR, FT-IR, UV-vis spectroscopy, powder X-ray diffractometry and thermogravimetric analysis. The ratio of β-cyclodextrin (β-CD units in CDP to PE was determined to be 2∶1. The KD value of the inclusion complex was determined to be 4.29×10(-3 mol•L(-1. In contrast to the low solubility of PE, the water-solubility of the PE-CDP complex was greatly enhanced. A preclinical toxicological study indicated that PE-CDP was well tolerated for a single administration. Importantly, the anti-inflammation potency of the PE-CDP complex was higher than that of PE. As a result, the formation of inclusion complexes by water-soluble CDP opens up possible aqueous applications of insoluble drug candidates in drug delivery.

  4. Supplementary Information DA conjugated polymers containing ...

    Indian Academy of Sciences (India)

    D-A conjugated polymers containing substituted thiophene, 1,3,4-oxadiazole and non-conjugation linkers: Synthesis and study of optical and electrochemical properties. PRASHANTH KUMAR K Ra, UDAYAKUMAR Da,*, SIJI NARENDRAN N Kb, CHANDRASEKHARAN Kb and RITU SRIVASTAVAc. aDepartment of ...

  5. Water soluble azido polyisocyanides as functional beta-sheet mimics

    NARCIS (Netherlands)

    Schwartz, Erik; Schwartz, E.; Koepf, Matthieu; Kitto, Heather J.; Espelt, Mónica; Nebot-Carda, Vicent J.; de Gelder, Rene; Nolte, Roeland J.M.; Cornelissen, Jeroen Johannes Lambertus Maria; Rowan, Alan E.

    2009-01-01

    The design and synthesis of functional biomimetic water soluble polymers with a defined secondary structure has been developed using β-sheet polyisocyanopeptide scaffolds. Water soluble isocyanopolymers were prepared by random copolymerisation of the azido functionalized isocyanopeptides with

  6. Effects of water-soluble natural antioxidants on photosensitized oxidation of conjugated linoleic acid in an oil-in-water emulsion system.

    Science.gov (United States)

    Liu, T-T; Yang, T-S

    2008-05-01

    The effect of photosensitized oxidation of conjugated linoleic acid in an oil-in-water (o/w) emulsion system was studied. Water-soluble natural antioxidants, including apple polyphenols from apple extract, green tea extract, 4-hydroxy-2(or 5)-ethyl-5(or2)-methyl-3(2H)-furanone(HEMF), 4-hydroxy-2,5-dimethyl-3(2H)-furanone (HDMF), and ascorbic acid, were tested for antioxidant activity in this system. The green tea extract showed the highest antioxidant activity followed by ascorbic acid. Apple polyphenols did not give significant antioxidant activity. HEMF and HDMF exhibited a prooxidant effect. The antioxidant activity of tea catechins was also investigated. Of them, EGCG and ECG exhibited antioxidant activity at 50 ppm, but the antioxidant activity between them was not significantly different (P < 0.05). Comparatively, EC, EGC, and GCG showed no significant antioxidative effect at 50 ppm. When the concentration increased to 100 ppm, the antioxidant activity of ECG and EGCG significantly increased compared with that at 50 ppm, and EGCG had higher antioxidant activity than ECG. GCG also showed significant antioxidant activity at 100 ppm. EGCG exhibited the highest antioxidant activity among the tea catechins in the emulsion system at 100 ppm.

  7. Conjugated Polymers as Actuators: Modes of Actuation

    DEFF Research Database (Denmark)

    Skaarup, Steen

    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....... This work discusses their relative merits and possible areas of application....

  8. 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....... This work discusses their relative merits and possible areas of application....

  9. Tight-binding treatment of conjugated polymers

    DEFF Research Database (Denmark)

    Lynge, Thomas Bastholm

    This PhD thesis concerns conjugated polymers which constitute a constantly growing research area. Today, among other things, conjugated polymers play a role in plastic based solar cells, photodetectors and light emitting diodes, and even today such plastic-based components constitute an alternative...... of tomorrow. This thesis specifically treats the three conjugated polymers trans-polyacetylene (tPA), poly(para-phenylene) (PPP) and poly(para-phe\\-nylene vinylene) (PPV). The present results, which are derived within the tight-binding model, are divided into two parts. In one part, analytic results...... are derived for the optical properties of the polymers expressed in terms of the optical susceptibility both in the presence and in the absence of a static electric field. In the other part, the cumputationally efficient Density Functional-based Tight-Binding (DFTB) model is applied to the description...

  10. The effect of water-soluble polymers, PEG and PVP, on the solubilisation of griseofulvin in aqueous micellar solutions of Pluronic F127.

    Science.gov (United States)

    Oliveira, Cristiane P; Ribeiro, Maria Elenir N P; Ricardo, Nágila M P S; Souza, Ticiane V de P; Moura, Carolina Lima; Chaibundit, Chiraphon; Yeates, Stephen G; Nixon, Keith; Attwood, David

    2011-12-15

    The purpose of this study was to investigate the possibility of enhancing the solubilisation capacity of micellar solutions of Pluronic F127 for the poorly water-soluble drug griseofulvin by co-formulating with a water-soluble polymer. The effect of the addition of the polyethylene glycols PEG6000 and 35000, and the poly(vinylpyrrolidone)s PVP K30 and K90, on the solubilisation capacity of 1wt% solutions of Pluronic F127 was related to the effect of these additives on particle size as determined by dynamic light scattering measurements. The addition of PEG35000 to 1wt% F127 solutions significantly increased the solubility capacity expressed in terms of unit weight of F127; PVP K90 had a smaller effect but no enhancement was noted following the addition of PEG6000 or PVP K30. Solubilisation enhancement was thought to be a consequence of the association of the polymers with the E-blocks of the micelle corona so providing an expanded region of reduced polarity for drug solubilisation. Copyright © 2011 Elsevier B.V. All rights reserved.

  11. Micelles based on methoxy poly(ethylene glycol)-cholesterol conjugate for controlled and targeted drug delivery of a poorly water soluble drug.

    Science.gov (United States)

    Li, Junming; He, Zhiyao; Yu, Shui; Li, Shuangzhi; Ma, Qing; Yu, Yiyi; Zhang, Jialin; Li, Rui; Zheng, Yu; He, Gu; Song, Xiangrong

    2012-10-01

    In this study, quercetin (QC) with cancer chemoprevention effect and anticancer potential was loaded into polymeric micelles of methoxy poly(ethylene glycol)-cholesterol conjugate (mPEG-Chol) in order to increase its water solubility. MPEG-Chol with lower critical micelle concentration (CMC) value (4.0 x 10(-7) M - 13 x 10(-7) M) was firstly synthesized involving two steps of chemical modification on cholesterol by esterification, and then QC was incorporated into mPEG-Chol micelles by self-assembly method. After the process parameters were optimized, QC-loaded micelles had higher drug loading (3.66%) and entrapment efficiency (93.51%) and nano-sized diameter (116 nm). DSC analysis demonstrated that QC had been incorporated non-covalently into the micelles and existed as an amorphous state or a solid solution in the polymeric matrix. The freeze-dried formulation with addition of 1% (w/v) mannitol as cryoprotectant was successfully developed for the long-term storage of QC-loaded micelles. Compared to free QC, QC-loaded micelles could release QC more slowly. Moreover, the release of QC from micelles was slightly faster in PBS at pH 5 than that in PBS at pH 7.4, which implied that QC-loaded micelles might be pH-sensitive and thereby selectively deliver QC to tumor tissue with unwanted side effects. Therefore, mPEG-Chol was a promising micellar vector for the controlled and targeted drug delivery of QC to tumor and QC-loaded micelles were also worth being further investigated as a potential formulation for cancer chemoprevention and treatment.

  12. Synthesis, characterization, and antiplasmodial activity of polymer-incorporated aminoquinolines

    CSIR Research Space (South Africa)

    Aderibigbe, BA

    2014-01-01

    Full Text Available In this research, aminoquinoline compounds were synthesized, characterized and incorporated into water soluble polymers to form conjugates. The conjugates were characterized by X ray Diffraction (XRD), Thermal Gravimetric Analysis (TGA), Scanning...

  13. Polymer conjugate of a microtubule destabilizer inhibits lung metastatic melanoma.

    Science.gov (United States)

    Yang, Ruinan; Mondal, Goutam; Ness, Rachel A; Arnst, Kinsie; Mundra, Vaibhav; Miller, Duane D; Li, Wei; Mahato, Ram I

    2017-03-10

    Melanoma is the most aggressive type of skin cancer. It is highly metastatic, migrating through lymph nodes to distant sites of the body, especially to lungs, liver and brain. Systemic chemotherapy remains the mainstay of treatment; however, the development of multidrug resistance (MDR) restricts the efficacy of current chemotherapeutic drugs. We synthesized a series of microtubule destabilizers, substituted methoxybenzoyl-ary-thiazole (SMART) compounds, which inhibited tubulin polymerization and effectively circumvented MDR. Due to poor water solubility of SMART compounds, co-solvent delivery is required for their systemic administration, which is usually associated with hepatotoxicity, nephrotoxicity and hemolysis. To solve this problem and also to increase circulation time, we synthesized a new SMART analogue, SMART-OH, and its polymer-drug conjugate, methoxy-poly (ethylene glycol)-block-poly (2-methyl-2-carboxyl-propylene carbonate-graft-SMART-graft-dodecanol) (abbreviated as P-SMART), with 14.3±2.8% drug payload of SMART-OH. Similar to its parent drug, P-SMART showed significant anticancer activity against melanoma cells in cytotoxicity, colony formation, and cell invasion studies. In addition, P-SMART treatment led to cell cycle arrest at G2/M phase and cell accumulation in sub-G1 phase. We established a model of metastatic melanoma to the lung in C57/BL6 albino mice to determine in vivo efficacy of P-SMART and SMART-OH at the dose of 20mg/kg. P-SMART treatment resulted in significant inhibition of tumor growth and prolonged mouse median survival. In conclusion, P-SMART, a novel polymer-microtubule destabilizer conjugate, has the potential to treat metastatic melanoma. Copyright © 2017 Elsevier B.V. All rights reserved.

  14. Electrochemical Deposition of Zinc Oxide on the Surface of Composite Membrane Polysulfone-Graphene-Polystyrene in the Presence of Water Soluble Polymers

    Directory of Open Access Journals (Sweden)

    Alexandra Mocanu

    2017-01-01

    Full Text Available The aim of this study consisted in the development of an alternative synthesis procedure for hybrid ultrafiltration membranes for water purification. The membranes were obtained by wet-phase inversion method based on aliquots of polysulfone (PSF and graphene nanoplatelets modified with poly(styrene (G-PST. The hybrid materials were modified by electrochemical deposition of zinc oxide (ZnO on one side of the membranes in the presence of water soluble polymers. Raman, XPS, and TGA analyses were used to characterize the chemical and thermal characteristics of the PST-G. SEM analysis showed the formation of asymmetric porous configuration in all cases and the generation of ZnO with different shapes/structures on the bottom surface of the membrane or inside the porous channels. EDS analysis confirmed the formation of ZnO.

  15. Theoretical study of conjugated porphyrin polymers

    DEFF Research Database (Denmark)

    Pedersen, T.G.; Lynge, T.B.; Kristensen, P.K.

    2005-01-01

    for these applications. From a theoretical analysis of excitons in long metalloporphyrin chains, we demonstrate that the binding energy is much lower than in usual conjugated polymers. Our calculated absorption spectra are in good agreement with measurements. (c) 2004 Elsevier B.V. All rights reserved....

  16. 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).

  17. 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...

  18. Fabrication of water-soluble polymer-encapsulated As4S4 to increase oral bioavailability and chemotherapeutic efficacy in AML mice

    Science.gov (United States)

    Ma, Qiang; Wang, Chuan; Li, Xiaojin; Guo, Hua; Meng, Jie; Liu, Jian; Xu, Haiyan

    2016-01-01

    Realgar (As4S4) has been demonstrated to be effective for the treatment of acute myeloid leukemia (AML); it has the advantages of no drug resistance and oral administration. Nevertheless, its poor solubility has been an obstacle to its bioavailability, requiring high-dose administration over a long period. We investigated whether crushing realgar crystals to the nanoscale and encapsulating the particles in a water-soluble polymer in one step using hot-melt extrusion would increase the bioavailability of As4S4. Raw As4S4 (r-As4S4) and water-soluble polymer were processed via co-rotating twin screw extrusion. The resulting product (e-As4S4) was characterized by SEM, XRD, and DLS. The cytotoxicity and therapeutic effects of e-As4S4 were evaluated in vivo and in vitro. The results show that e-As4S4 dissolved rapidly in water, forming a stable colloid solution. The average size of e-As4S4 particles was 680 nm, which was reduced by more than 40-fold compared with that of r-As4S4. The bioavailability of e-As4S4 was up to 12.6-fold higher than that of r-As4S4, and it inhibited the proliferation of HL-60 cells much more effectively than did r-As4S4, inducing apoptosis and significantly reducing the infiltration of HL-60 cells into the bone marrow, spleen, and liver. This in turn prolonged the survival of AML mice. PMID:27383126

  19. Composites based on cellulose fiber nonwovens and a water-soluble polymer 2. Strength-deformation characteristics of the composites

    Science.gov (United States)

    Cerpakovska, D.; Kalnins, M.

    2012-09-01

    The relationship between the strength-deformation properties and certain structural characteristics (volume content of polymer and voids, orientation of fibers) of composites prepared by impregnation of cellulose fiber nonwovens (CFNs) with poly(vinyl alcohol) water solutions is discussed. With growth in the volume fraction of polymer to 0.25-0.30, the tensile elastic modulus and ultimate strength of the composites increase compared with those of CFN. As a consequence of enhanced adhesion among the cellulose fibers, the relative values of tensile strength and elastic modulus in the main orientation direction of the fibers is higher than in the perpendicular one. Therefore, with increasing content of polymer in the composite, its degree of anisotropy diminishes significantly. The punching strength almost linearly correlates with the tensile strength. The breaking strain in tension increases considerably with growing content of polymer, but the tearing strength changes only slightly.

  20. Five water-soluble zwitterionic copper(II)-carboxylate polymers: role of dipyridyl coligands in enhancing the DNA-binding, cleaving and anticancer activities.

    Science.gov (United States)

    Chen, Ming; Tang, Xiao-Yan; Yang, Shui-Ping; Li, Huan-Huan; Zhao, Hai-Qing; Jiang, Zhi-Hong; Chen, Jin-Xiang; Chen, Wen-Hua

    2015-08-07

    Five water-soluble zwitterionic copper-carboxylate polymers were prepared from the reaction of N-carboxymethyl-(3,5-dicarboxyl)pyridinium bromide (H3CmdcpBr) with Cu(NO3)2 in the presence of NaOH by modulating the temperature, solvent and ancillary dipyridyl ligands. These complexes include a 1D ladder-shaped polymer {[Cu3(Cmdcp)2(OH)2(H2O)2]·H2O}n () formed in H2O at room temperature, and a 2D network polymer {[Cu(Cmdcp) (H2O)2]·2H2O}n () isolated in H2O at 135 °C. At 100 °C in H2O/DMF, the same reaction in the presence of an additional 2,2'-bipyridine (bipy) gave a 2D zwitterionic complex {[Cu(Cmdcp)(bipy)]·3H2O}n () together with a 1D double-stranded polymer {[Cu(Cmdcp)(H2O)2]·H2O}n () as a minor product. The replacement of bipy with phenanthroline (phen) afforded a 1D zigzag polymer chain {[Cu(Cmdcp)(phen)(H2O)]2·9H2O}5 (). All these complexes were characterized by IR, elemental analyses and single crystal X-ray crystallography. Agarose gel electrophoresis (GE) and ethidium bromide (EB) displacement experiments indicated that complex exhibited the highest pBR322 DNA cleaving ability with the catalytic efficiency (kmax/KM) of 14.80 h(-1) mM(-1) and the highest binding affinity toward calf-thymus DNA. The MTT assay indicated that complex showed significant inhibitory activity toward the proliferation of several tumor cells. Its IC50 value was at micromolar level and lower than those of cisplatin and complexes , especially toward resistant lung adenocarcinoma cell A549.

  1. Selective recognition and discrimination of water-soluble azo dyes by a seven-channel molecularly imprinted polymer sensor array.

    Science.gov (United States)

    Long, Zerong; Lu, Yi; Zhang, Mingliang; Qiu, Hongdeng

    2014-10-01

    A seven-channel molecularly imprinted polymer sensor array was prepared and characterized by scanning electron microscopy, Fourier transform infrared spectroscopy, UV-Vis spectroscopy, and nitrogen physisorption studies. The results revealed that the imprinted polymers have distinct-binding affinities from those of structurally similar azo dyes. Analysis of the UV-Vis spectral response patterns of the seven dye analytes against the imprinted polymer array suggested that the different selectivity patterns of the array were closely connected to the imprinting process. To evaluate the effectiveness of the array format, the binding of a series of analytes was individually measured for each of the seven polymers, made with different templates (including one control polymer synthesized without the use of a template). The response patterns of the array to the selected azo dyes were processed by canonical discriminant analysis. The results showed that the molecularly imprinted array was able to discriminate each analyte with 100% accuracy. Moreover, the azo dyes in two real samples, spiked chrysoidin in smoked bean curd extract and Fanta lime soda (containing tartrazine), were successfully classified by the array. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. A novel water-soluble fluorescent polymer based on perylene bisimides dyes: one-pot preparation and its bio-imaging.

    Science.gov (United States)

    Tan, Haijian; Liu, Hongmei; Liu, Yaojun; Duan, Wenfeng; Yi, Xuegang; Wu, Yonggang; Zhao, Hongchi; Bai, Libin

    2016-01-01

    Perylene bisimides dye-based water-soluble fluorescent polymer P3, N,N'-bis(3-amyl)-1-bromo-7-{4'-[3''-(S-poly(N-acryloyl ethylene diamine hydrochloride)-2'''-methyl propionic acid)propionyloxy hexyloxy]phenyl} perylene-3,4:9,10-tetracarboxylic bisimides, was synthesized with polyelectrolyte modification via one-pot reaction (the reduction reaction of trithioester and click reaction between the thiol group and carbon-carbon double bond were simultaneously conducted in one pot with high conversion). One-pot method can overcome the limitation that usual click reaction between thiol and other groups has low conversion because thiol group is subject to rapid oxidation during purification and storage. Chemical, structural, and optical properties of P3 and intermediate products were fully characterized by nuclear magnetic resonance spectroscopy, Fourier transform infrared, gel permeation chromatograph, UV-vis spectra, and fluorescence spectra, respectively. The results revealed that P3 displayed excellent water solubility and not only exhibited red strong fluorescence emission band in water but also had the similar photoluminescent spectra to those of intermediate products (M4 and P2) in chloroform. Allowing for the potential application in biological detection field, cell viability and live cell imaging with the presence of P3 were further investigated with Hela cells. The results showed that P3 had low cytotoxicity with strong intracellular fluorescence entry. Meanwhile, with the augment of concentration of P3 (0-0.500 mg mL(-1)), the cell uptake and accumulation of P3 increased and thereby result in enhancement of the intracellular fluorescence. These experiment results suggested that P3 had enormous potential as a fluorescence probe to be an important component in biological detection field.

  3. Biodegradable Micellar HPMA-Based Polymer-Drug Conjugates with Betulinic Acid for Passive Tumor Targeting.

    Science.gov (United States)

    Lomkova, Ekaterina A; Chytil, Petr; Janoušková, Olga; Mueller, Thomas; Lucas, Henrike; Filippov, Sergey K; Trhlíková, Olga; Aleshunin, Pavel A; Skorik, Yury A; Ulbrich, Karel; Etrych, Tomáš

    2016-11-14

    Here, we present the synthesis, physicochemical, and preliminary biological characterization of micellar polymer-betulinic acid (BA) conjugates based on N-(2-hydroxypropyl)methacrylamide (HPMA) copolymer carriers, enabling the controlled release of cytotoxic BA derivatives in solid tumors or tumor cells. Various HPMA copolymer conjugates differing in the structure of the spacer between the drug and the carrier were synthesized, all designed for pH-triggered drug release in tumor tissue or tumor cells. The high molecular weight of the micellar conjugates should improve the uptake of the drug in solid tumors due to the Enhanced permeability and retention (EPR) effect. Nevertheless, only the conjugate containing BA with methylated carboxyl groups enabled pH-dependent controlled release in vitro. Moreover, drug release led to the disassembly of the micellar structure, which facilitated elimination of the water-soluble HPMA copolymer carrier from the body by renal filtration. The methylated BA derivative and its polymer conjugate exhibited high cytostatic activity against DLD-1, HT-29, and HeLa carcinoma cell lines and enhanced tumor accumulation in HT-29 xenograft in mice.

  4. Self-Doped Conjugated Polymer as Binders for Lithium-ion Battery Cathode

    Science.gov (United States)

    Li, Xiaoyi; An, Hyosung; Lutkenhaus, Jodie; Verduzco, Rafael

    Water-soluble, self-doped conjugated polymers have been reported to have good electrical conductivity, making them potentially strong candidates for energy storage and organic solar cell applications. In this work, two types of self-doped polymers with different pi-conjugated backbones were developed and studied systematically as organic multi-functional polymeric binders for V2O5 cathode in lithium-ion batteries: PFP with fluorene-phenol backbone, and PCPDTBTSO3K with cyclopenta-[2,1-b3,4-b']-dithiophene-alt-4,7-(2,1,3-benzothiadiazole) backbone. A series of ex-stu thermal annealing experiment was carried out to investigate the structural impacts of incorporating self-doped polymers into V2O5 electrode at high temperature. X-ray powder diffraction (XRD) and grazing-incidence wide-angle x-ray scattering (GIWAXS) showed clear evidence that addition of only 5wt% polymer can suppress V2O5 crystallization up to 450° C. Electrochemical tests of V2O5/polymer hybrid electrodes showed best capacity improvement at 250° C ( 190 mAh/g for 5wt% PFP addition), alongside with enhancement in rate performance and charge-transport in thicker electrodes. Peel test was conducted with varying polymer content to show how these polymeric binders improve electrode adhesion. NSF.

  5. Crosslinked polymer nanoparticles containing single conjugated polymer chains

    Science.gov (United States)

    Ponzio, Rodrigo A.; Marcato, Yésica L.; Gómez, María L.; Waiman, Carolina V.; Chesta, Carlos A.; Palacios, Rodrigo E.

    2017-06-01

    Conjugated polymer nanoparticles are widely used in fluorescent labeling and sensing, as they have mean radii between 5 and 100 nm, narrow size dispersion, high brightness, and are photochemically stable, allowing single particle detection with high spatial and temporal resolution. Highly crosslinked polymers formed by linking individual chains through covalent bonds yield high-strength rigid materials capable of withstanding dissolution by organic solvents. Hence, the combination of crosslinked polymers and conjugated polymers in a nanoparticulated material presents the possibility of interesting applications that require the combined properties of constituent polymers and nanosized dimension. In the present work, F8BT@pEGDMA nanoparticles composed of poly(ethylene glycol dimethacrylate) (pEGDMA; a crosslinked polymer) and containing the commercial conjugated polymer poly(9,9-dioctylfluorene-alt-benzothiadiazole) (F8BT) were synthesized and characterized. Microemulsion polymerization was applied to produce F8BT@pEDGMA particles with nanosized dimensions in a ∼25% yield. Photophysical and size distribution properties of F8BT@pEDGMA nanoparticles were evaluated by various methods, in particular single particle fluorescence microscopy techniques. The results demonstrate that the crosslinking/polymerization process imparts structural rigidity to the F8BT@pEDGMA particles by providing resistance against dissolution/disintegration in organic solvents. The synthesized fluorescent crosslinked nanoparticles contain (for the most part) single F8BT chains and can be detected at the single particle level, using fluorescence microscopy, which bodes well for their potential application as molecularly imprinted polymer fluorescent nanosensors with high spatial and temporal resolution.

  6. Investigation of some locally water-soluble natural polymers as circulation loss control agents during oil fields drilling

    Directory of Open Access Journals (Sweden)

    A.M. Alsabagh

    2014-03-01

    Full Text Available Eliminating or controlling lost circulation during drilling process is costly and time-consuming. Polymers play an important role in mud loss control for their viscosity due to their high molecular weight. In this paper, three natural cellulosic polymers (carboxymethyl cellulose, guar gum and potato starch were investigated as lost circulation control material by measuring different filtration parameters such as; spurt loss, fluid loss and permeability plugging tester value according to the American Petroleum Institute (API standard. The experiments were conducted in a permeability plugging apparatus (PPA at a differential pressure of 100 and 300 psi, using 10, 60 and 90 ceramic discs. From the obtained data, it was found that the 0.1% from the carboxymethyl cellulose exhibited the best results in the filtration parameters among 0.3% guar gum and 0.6% potato starch. At the same time the carboxymethyl cellulose (CMC enhanced the rheological properties of the drilling mud better than the two other used natural polymers in the term of gel strength, thixotropy, plastic and apparent viscosity. These results were discussed in the light of the adsorption and micellar formation.

  7. Design, synthesis, characterization and study of novel conjugated polymers

    Energy Technology Data Exchange (ETDEWEB)

    Chen, Wu [Iowa State Univ., Ames, IA (United States)

    1997-06-24

    After introducing the subject of conjugated polymers, the thesis has three sections each containing a literature survey, results and discussion, conclusions, and experimental methods on the following: synthesis, characterization of electroluminescent polymers containing conjugated aryl, olefinic, thiophene and acetylenic units and their studies for use in light-emitting diodes; synthesis, characterization and study of conjugated polymers containing silole unit in the main chain; and synthesis, characterization and study of silicon-bridged and butadiene-linked polythiophenes.

  8. Responsive Guest Encapsulation of Dynamic Conjugated Microporous Polymers.

    Science.gov (United States)

    Xu, Lai; Li, Youyong

    2016-06-30

    The host-guest complexes of conjugated microporous polymers encapsulating C60 and dye molecules have been investigated systematically. The orientation of guest molecules inside the cavities, have different terms: inside the open cavities of the polymer, or inside the cavities formed by packing different polymers. The host backbone shows responsive dynamic behavior in order to accommodate the size and shape of incoming guest molecule or guest aggregates. Simulations show that the host-guest binding of conjugated polymers is stronger than that of non-conjugated polymers. This detailed study could provide a clear picture for the host-guest interaction for dynamic conjugated microporous polymers. The mechanism obtained could guide designing new conjugated microporous polymers.

  9. Carbamazepine solubility enhancement in tandem with swellable polymer osmotic pump tablet: A promising approach for extended delivery of poorly water-soluble drugs

    Directory of Open Access Journals (Sweden)

    Hadjira Rabti

    2014-06-01

    Full Text Available Elementary osmotic pump (EOP is a unique extended release (ER drug delivery system based on the principle of osmosis. It has the ability to minimize the amount of the drug, accumulation and fluctuation in drug level during chronic uses. Carbamazepine (CBZ, a poorly water-soluble antiepileptic drug, has serious side effects on overdoses and chronic uses. The aim of the present study was to design a new EOP tablet of CBZ containing a solubility enhancers and swellable polymer to reduce its side effects and enhance the patient compliance. Firstly, a combination of solubilizing carriers was selected to improve the dissolution of the slightly soluble drug. Then, designing the new EOP tablet and investigating the effect of different variables of core and coat formulations on drug release behavior by single parameter optimization and by Taguchi orthogonal design with analysis of variance (ANOVA, respectively. The results showed that CBZ solubility was successfully enhanced by a minimum amount of combined polyvinyl pyrrolidone (PVP K30 and sodium lauryl sulfate (SLS. The plasticizer amount and molecular weight (MW together with the osmotic agent amount directly affect the release rate whereas the swellable polymer amount and viscosity together with the semi-permeable membrane (SPM thickness inversely influence the release rate. In addition, the tendency of following zero order kinetics was mainly affected by the coat components rather than those of the core. Further, orifice size does not have any significant effect on the release behavior within the range of 0.1 mm to 0.8 mm. In this study we report the successful formulation of CBZ-EOP tablets, which were similar to the marketed product Tegretol CR 200 and able to satisfy the USP criterion limits and to deliver about 80% of CBZ at a rate of approximately zero order for up to 12 h.

  10. Thiophene-based donor–acceptor conjugated polymer as potential ...

    Indian Academy of Sciences (India)

    The polymer solution, polymer film and polymer/TiO2 nanocomposite film show a strong saturable absorption behaviour. The value of saturation intensity (Is) is found to be of the order 1011–1012 W/m2, indicating that the materials are useful candidates for photonic applications. Keywords. Conjugated polymer; cyclic ...

  11. A detailed study on the interaction of a novel water-soluble glycine bridged zinc(II) Schiff base coordination polymer with BSA: synthesis, crystal structure, molecular docking and cytotoxicity effect against A549, Jurkat and Raji cell lines

    Czech Academy of Sciences Publication Activity Database

    Asadi, Z.; Golchin, M.; Eigner, Václav; Dušek, Michal; Amirghofran, Z.

    2017-01-01

    Roč. 465, Aug (2017), s. 50-60 ISSN 0020-1693 R&D Projects: GA MŠk LO1603; GA ČR(CZ) GA14-03276S EU Projects: European Commission(XE) CZ.2.16/3.1.00/24510 Institutional support: RVO:68378271 Keywords : water-soluble * coordination polymer * BSA * docking study * anticancer activity Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 2.002, year: 2016

  12. Conjugated Microporous Polymers for Heterogeneous Catalysis.

    Science.gov (United States)

    Zhou, Yun-Bing; Zhan, Zhuang-Ping

    2018-01-04

    Conjugated microporous polymers (CMPs) are a class of crosslinked polymers that combine permanent micropores with π-conjugated skeletons and possess three-dimensional (3D) networks. Compared with conventional materials such as metal-organic frameworks (MOFs) and covalent organic frameworks (COFs), CMPs usually have superior chemical and thermal stability. CMPs have made significant progress in heterogeneous catalysis in the past seven years. With a bottom-up strategy, catalytic moieties can be directly introduced into in the framework to produce heterogeneous CMP catalysts. Higher activity, stability, and selectivity can be obtained with heterogeneous CMP catalysts in comparison with their homogeneous analogs. In addition, CMP catalysts can be easily isolated and recycled. In this review, we focus on CMPs as an intriguing platform for developing various highly efficient and recyclable heterogeneous catalysts in organic reactions. The design, synthesis, and structure of these CMP catalysts are also discussed in this focus review. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  13. Synthesis and characterization of a novel molecularly imprinted polymer for simultaneous extraction and determination of water-soluble and fat-soluble synthetic colorants in chilli products by solid phase extraction and high performance liquid chromatography.

    Science.gov (United States)

    Long, Chaoyang; Mai, Zhibin; Yang, Yingfen; Zhu, Binghui; Xu, Xiumin; Lu, Lin; Zou, Xiaoyong

    2009-11-20

    A sorbent was synthesized and investigated for molecularly imprinted solid phase extraction (MISPE). Molecularly imprinted polymers (MIP) were synthesized via precipitation polymerization procedure, where 4-vinyl pyridine (4-VP) was used as functional monomer and ethylene glycol dimethacrylate (EDMA) as cross-linking agent. The imprinting effect of the MISPE was evaluated by elution experiments. The resulting MISPE showed high extraction selectivity to water-soluble and fat-soluble synthetic colorants. The determination of multi-residue for three kinds of water-soluble and six kinds of fat-soluble synthetic colorants in chilli products was also investigated by HPLC coupled with MISPE. The mean recoveries calculated by solvent calibration curve for water-soluble and fat-soluble synthetic colorants were from 72.1% to 95.6% for chilli spice and 72.1% to 92.3% for chilli powder. The decision limit (CCalpha) and the detection capability (CCbeta) obtained for water-soluble and fat-soluble synthetic colorants were in the range of 1.2-1.6 and 1.9-2.4 microg kg(-1) in chilli spice and chilli powder. The resulting MISPE was successfully used off-line for the determination of nine kinds of synthetic colorants in chilli products.

  14. Fabrication of Conjugated Polymer Nanowires by Edge Lithography

    NARCIS (Netherlands)

    Lipomi, Darren J.; Chiechi, Ryan C.; Dickey, Michael D.; Whitesides, George M.

    2008-01-01

    This paper describes the fabrication of conjugated polymer nanowires by a three stage process: (i) spin-coating a composite film comprising alternating layers of a conjugated polymer and a sacrificial material, (ii) embedding the film in an epoxy matrix and sectioning it with an ultramicrotome

  15. 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.

  16. Identification of excited states in conjugated polymers

    CERN Document Server

    Hartwell, L J

    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 instrument was developed and optimised for each different sample. Lock-i...

  17. 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.

  18. A New FRET-Based Sensitive DNA Sensor for Medical Diagnostics using PNA Probe and Water-Soluble Blue Light Emitting Polymer

    Directory of Open Access Journals (Sweden)

    Nidhi Mathur

    2008-01-01

    Full Text Available A reliable, fast, and low-cost biosensor for medical diagnostics using DNA sequence detection has been developed and tested for the detection of the bacterium “Bacillus anthracis.” In this sensor, Poly [9,9-di (6,6′- N, N′ trimethylammonium hexylfluorenyl-2, 7-diyl-alt-co- (1,4-phenylene] dibromide salt (PFP has been taken as cationic conjugated polymer (CCP and PNA attached with fluorescein dye (PNAC∗ as a probe. The basic principle of this sensor is that when a PNAC∗ probe is hybridized with a single strand DNA (ssDNA having complementary sequence, Forster resonance energy transfer (FRET may take place from PFP to the PNAC∗/DNA complex. If the FRET is efficient, the photoluminescence from the PFP will be highly quenched and that from PNAC∗ will be enhanced. On the other hand, if the DNA sequence is noncomplementary to PNA, FRET will not occur.

  19. Photophysical Studies of Ring Containing Conjugated Polymers

    Science.gov (United States)

    Lin, Liangbih

    Ultrafast and cw spectroscopy of ring-containing conjugated polymers, in particular, leucoemeraldine (LEB), emeraldine (EB) and pernigraniline bases (PNB) of polyaniline, and poly(p-pyridine)(PPy), are investigated. The important roles of ring-torsional degrees of freedom were demonstrated by investigating the dynamics of photoexcitations in restrained (solid) and unrestrained (solution) environments. When excited into the 2.0 eV exciton band (EB) or the 2.3 eV Peierls gap (PNB), the photoexcited species in NMP solution decayed within 30 ps. However, under similar experimental conditions, a long-lived component (>ns) appeared in solid samples of EB and PNB. For EB, the 2.9 eV polaron (rm P_{B}^ {+}) lasted longer than the exciton ( tau_{rm polaron}>tau _{rm exciton}). The situation was reversed for PNB, in which the polarons decayed faster than the recovery of the ground state. Comparing the PIA results, the lifetime of the polaron follows: tau_{polaron} (LEB)> tau _{polaron} (EB)>tau_{polaron }(PNB). These results strongly suggest that the quinoid moiety in polyaniline is acting as a quenching site for P_{B}^ {+}. Intensity dependence studies have revealed that the decay mechanism is mainly unimolecular for both the 2.0 eV band (PIB) and the 2.9 eV band (PIA) of EB and PNB. It appears that in polyaniline the confinement length is longer than the decay length of the 2. 1 eV photoexcitation. Photoluminescence (PL) studies of PPy have confirmed the notion that optically active species in conjugated polymers are comprised of sub-units of the chain likely separated by topological defects. The PL of PPy features a minimum Stokes shift when chains of the polymer are unrestrained, such as in solution. Whereas, a persistent apparent Stokes shift is present for the PL occurring in a confined environment, such as films. Phosphorescence and fluorescence of rm (n-pi*)^1 state were detected at photoexcitation energies significantly above the band edge for PPy/ITO/glass films

  20. Magnetism in (Semi)Conducting Macrocycles of pi conjugated Polymers

    Science.gov (United States)

    2016-12-09

    AFRL-AFOSR-JP-TR-2017-0006 Magnetism in (Semi)Conducting Macrocycles of pi-conjugated Polymers Andre Persoons KATHOLIEKE UNIVERSITEIT TE LEUVEN INST...Macrocycles of pi-conjugated Polymers 5a.  CONTRACT NUMBER 5b.  GRANT NUMBER FA2386-15-1-4051 5c.  PROGRAM ELEMENT NUMBER 61102F 6. AUTHOR(S) Andre Persoons...the investigation of potential magnetic properties of macrocycles of pi-conjugated polymers . This research was initially motivated by the observation

  1. 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.

  2. Recent Advances in Conjugated Polymers for Light Emitting Devices

    Directory of Open Access Journals (Sweden)

    Mohan Raja

    2011-03-01

    Full Text Available 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.

  3. 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

  4. Glycyrrhetinic acid-poly(ethylene glycol)-glycyrrhetinic acid tri-block conjugates based self-assembled micelles for hepatic targeted delivery of poorly water soluble drug.

    Science.gov (United States)

    Wu, Fengbo; Xu, Ting; Liu, Chi; Chen, Can; Song, Xiangrong; Zheng, Yu; He, Gu

    2013-01-01

    The triblock 18β-glycyrrhetinic acid-poly(ethylene glycol)18β-glycyrrhetinic acid conjugates (GA-PEG-GA) based self-assembled micelles were synthesized and characterized by FTIR, NMR, transmission electron microscopy, and particle size analysis. The GA-PEG-GA conjugates having the critical micelle concentration of 6 × 10(-5) M were used to form nanosized micelles, with mean diameters of 159.21 ± 2.2 nm, and then paclitaxel (PTX) was incorporated into GA-PEG-GA micelles by self-assembly method. The physicochemical properties of the PTX loaded GA-PEG-GA micelles were evaluated including in vitro cellular uptake, cytotoxicity, drug release profile, and in vivo tissue distribution. The results demonstrate that the GA-PEG-GA micelles had low cytotoxicity and good ability of selectively delivering drug to hepatic cells in vitro and in vivo by the targeting moiety glycyrrhetinic acid. In conclusion, the GA-PEG-GA conjugates have potential medical applications for targeted delivery of poor soluble drug delivery.

  5. Two-Photon Photosensitizer-Polymer Conjugates for Combined Cancer Cell Death Induction and Two-Photon Fluorescence Imaging: Structure/Photodynamic Therapy Efficiency Relationship.

    Science.gov (United States)

    Cepraga, Cristina; Marotte, Sophie; Ben Daoud, Edna; Favier, Arnaud; Lanoë, Pierre-Henri; Monnereau, Cyrille; Baldeck, Patrice; Andraud, Chantal; Marvel, Jacqueline; Charreyre, Marie-Thérèse; Leverrier, Yann

    2017-11-10

    One of the challenges of photodynamic therapy is to increase the penetration depth of light irradiation in the tumor tissues. Although two-photon excitation strategies have been developed, the two-photon absorption cross sections of clinically used photosensitizers are generally low (below 300 GM). Besides, photosensitizers with high cross section values are often non-water-soluble. In this research work, a whole family of photosensitizer-polymer conjugates was synthesized via the covalent binding of a photosensitizer with a relatively high cross section along a biocompatible copolymer chain. The resulting photosensitizer-polymer conjugates were water-soluble and could be imaged in cellulo by two-photon microscopy thanks to their high two-photon absorption cross sections (up to 2600 GM in water, in the NIR range). In order to explore the structure/photodynamic activity relationship of such macromolecular photosensitizers, the influence of the polymer size, photosensitizer density, and presence of charges along the polymer backbone was investigated (neutral, anionic, cationic, and zwitterionic conjugates were compared). The macromolecular photosensitizers were not cytotoxic in the absence of light irradiation. Their kinetics of cellular uptake in the B16-F10 melanoma cell line were followed by flow cytometry over 24 h. The efficiency of cell death upon photoactivation was found to be highly correlated to the cellular uptake in turn correlated to the global charge of the macromolecular photosensitizer which appeared as the determining structural parameter.

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

    African Journals Online (AJOL)

    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 ...

  7. Aqueous Processing for Printed Organic Electronics: Conjugated Polymers with Multistage Cleavable Side Chains.

    Science.gov (United States)

    Schmatz, Brian; Yuan, Zhibo; Lang, Augustus W; Hernandez, Jeff L; Reichmanis, Elsa; Reynolds, John R

    2017-09-27

    The ability to process conjugated polymers via aqueous solution is highly advantageous for reducing the costs and environmental hazards of large scale roll-to-roll processing of organic electronics. However, maintaining competitive electronic properties while achieving aqueous solubility is difficult for several reasons: (1) Materials with polar functional groups that provide aqueous solubility can be difficult to purify and characterize, (2) many traditional coupling and polymerization reactions cannot be performed in aqueous solution, and (3) ionic groups, though useful for obtaining aqueous solubility, can lead to a loss of solid-state order, as well as a screening of any applied bias. As an alternative, we report a multistage cleavable side chain method that combines desirable aqueous processing attributes without sacrificing semiconducting capabilities. Through the attachment of cleavable side chains, conjugated polymers have for the first time been synthesized, characterized, and purified in organic solvents, converted to a water-soluble form for aqueous processing, and brought through a final treatment to cleave the polymer side chains and leave behind the desired electronic material as a solvent-resistant film. Specifically, we demonstrate an organic soluble polythiophene that is converted to an aqueous soluble polyelectrolyte via hydrolysis. After blade coating from an aqueous solution, UV irradiation is used to cleave the polymer's side chains, resulting in a solvent-resistant, electroactive polymer thin film. In application, this process results in aqueous printed materials with utility for solid-state charge transport in organic field effect transistors (OFETs), along with red to colorless electrochromism in ionic media for color changing displays, demonstrating its potential as a universal method for aqueous printing in organic electronics.

  8. 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.

  9. Thermo-reversible morphology and conductivity of a conjugated polymer network embedded in polymeric self-assembly

    Science.gov (United States)

    Han, Youngkyu; Carrillo, Jan-Michael Y.; Zhang, Zhe; Li, Yunchao; Hong, Kunlun; Sumpter, Bobby G.; Ohl, Michael; Paranthaman, Mariappan Parans; Smith, Gregory S.; Do, Changwoo

    Self-assembly of block copolymers provides opportunities to create nano hybrid materials, utilizing self-assembled micro-domains with a variety of morphology and periodic architectures as templates for functional nano-fillers. Here we report new progress towards the fabrication of a thermally responsive conducting polymer self-assembly made from a water-soluble poly(thiophene) derivative with short PEO side chains and Pluronic L62 solution in water. The structural and electrical properties of conjugated polymer-embedded nanostructures were investigated by combining SANS, SAXS, CGMD simulations, and impedance spectroscopy. The L62 solution template organizes the conjugated polymers by stably incorporating them into the hydrophilic domains thus inhibiting aggregation. The changing morphology of L62 during the micellar-to-lamellar phase transition defines the embedded conjugated polymer network. The conductivity is strongly coupled to the structural change of the templating L62 phase and exhibits thermally reversible behavior with no signs of quenching of the conductivity at high temperature. The research was sponsored by the Scientific User Facilities Division, Office of BES, U.S. DOE and Laboratory Directed Research and Development Program of ORNL, managed by UT-Battelle, LLC.

  10. 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.

  11. Aqueous Processing for Printed Organic Electronics: Conjugated Polymers with Multistage Cleavable Side Chains

    Science.gov (United States)

    2017-01-01

    The ability to process conjugated polymers via aqueous solution is highly advantageous for reducing the costs and environmental hazards of large scale roll-to-roll processing of organic electronics. However, maintaining competitive electronic properties while achieving aqueous solubility is difficult for several reasons: (1) Materials with polar functional groups that provide aqueous solubility can be difficult to purify and characterize, (2) many traditional coupling and polymerization reactions cannot be performed in aqueous solution, and (3) ionic groups, though useful for obtaining aqueous solubility, can lead to a loss of solid-state order, as well as a screening of any applied bias. As an alternative, we report a multistage cleavable side chain method that combines desirable aqueous processing attributes without sacrificing semiconducting capabilities. Through the attachment of cleavable side chains, conjugated polymers have for the first time been synthesized, characterized, and purified in organic solvents, converted to a water-soluble form for aqueous processing, and brought through a final treatment to cleave the polymer side chains and leave behind the desired electronic material as a solvent-resistant film. Specifically, we demonstrate an organic soluble polythiophene that is converted to an aqueous soluble polyelectrolyte via hydrolysis. After blade coating from an aqueous solution, UV irradiation is used to cleave the polymer’s side chains, resulting in a solvent-resistant, electroactive polymer thin film. In application, this process results in aqueous printed materials with utility for solid-state charge transport in organic field effect transistors (OFETs), along with red to colorless electrochromism in ionic media for color changing displays, demonstrating its potential as a universal method for aqueous printing in organic electronics. PMID:28979937

  12. Temperature dependence of exciton diffusion in conjugated polymers

    NARCIS (Netherlands)

    Mikhnenko, O.V.; Cordella, F.; Sieval, A.B.; Hummelen, J.C.; Blom, P.W.M.; Loi, M.A.

    2008-01-01

    The temperature dependence of the exciton dynamics in a conjugated polymer is studied using time-resolved spectroscopy. Photoluminescence decays were measured in heterostructured samples containing a sharp polymer-fullerene interface, which acts as an exciton quenching wall. Using a ID diffusion

  13. Synthesis of regioregular pentacene-containing conjugated polymers

    KAUST Repository

    Okamoto, Toshihiro

    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.

  14. 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...... demonstrate how microscopic ordering in the polymer domains controls the conductivity....

  15. Toward High Performance Photovoltaic Cells based on Conjugated Polymers

    Science.gov (United States)

    2016-12-26

    AFRL-AFOSR-JP-TR-2016-0103 Toward High Performance Photovoltaic Cells based on Conjugated Polymers Kung-Hwa Wei National Chiao Tung University Final...Conjugated Polymers 5a.  CONTRACT NUMBER 5b.  GRANT NUMBER FA2386-15-1-4113 5c.  PROGRAM ELEMENT NUMBER 61102F 6. AUTHOR(S) Kung-Hwa Wei 5d.  PROJECT...gap polymer with good packing order as the active layer for a single-junction photovoltaic device. The light absorptions for the small molecule and the

  16. Formation and characterization of stable fluorescent complexes between neutral conjugated polymers and cyclodextrins.

    Science.gov (United States)

    Martínez-Tomé, Maria José; Esquembre, Rocío; Mallavia, Ricardo; Mateo, C Reyes

    2013-01-01

    Solubilisation and stabilization of conjugated polymers, CPs, in aqueous media remains a challenge for many researches trying to extend the biological and environmental applications of this kind of polymers. A number of different alternatives have been considered to address this problem, which are mostly based on the enhancement of the macromolecule polarity, by appending hydrophilic side chains on the polymer backbone. In this work we have investigated a new strategy in which water solubilization is reached by external addition of classical cyclodextrins (α-, β- and γ-CDs) to a solution of non-polar CPs. This strategy allows working with such polymers eliminating the need to synthesize new water-soluble species. The polymer selected for the study was poly-[9,9-bis(6'-bromohexyl-2,7-fluoren-dyil)-co-alt-(benzene-1,4-diy)], PFPBr(2), a polyfluorene previously synthesized in our laboratory. Results show that PFPBr(2) forms fluorescent complexes in aqueous media with β-CD and γ-CD, and much less efficiently with α-CD, probably due to the small size of its cavity. The new PFPBr(2)/CD complexes are stable in time and in a large range of pH, however, at high concentration and temperature, they tend to aggregate and precipitate. In order to increase stabilization and minimize polymer aggregation, complexes were encapsulated inside the pores of silica glasses fabricated using the sol-gel process, obtaining transparent and fluorescent hybrid matrices which were stable in time and temperature. In addition, immobilization of the complexes allows an easy manipulation of the material, thus offering promising applications in the development of biological and chemical sensors.

  17. Conjugated polymer-porphyrin complexes for organic electronics.

    Science.gov (United States)

    Andernach, Rolf E; Rossbauer, Stephan; Ashraf, Raja S; Faber, Hendrik; Anthopoulos, Thomas D; McCulloch, Iain; Heeney, Martin; Bronstein, Hugo A

    2015-04-27

    We present the synthesis of novel conjugated polymer-porphyrin complexes for use in organic electronics. Linear and star-shaped platinated porphyrins were attached to regioregular poly(3-hexylthiophene-2,5-diyl) (P3HT) arms to investigate whether porphyrin stacking and increased dimensionality can be used to control polymer morphology. The novel materials display similar optical properties to P3HT, but give higher mobilities when used in organic field-effect transistors. Atomic force microscopy measurements show that incorporation of only a small amount of porphyrin into the conjugated polymer backbone leads to increased aggregation. These materials demonstrate that polymer morphology and performance can be tuned and enhanced effectively through the use of conjugatively linked porphyrins. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. Responsive Guest Encapsulation of Dynamic Conjugated Microporous Polymers

    OpenAIRE

    Lai Xu; Youyong Li

    2016-01-01

    The host-guest complexes of conjugated microporous polymers encapsulating C60 and dye molecules have been investigated systematically. The orientation of guest molecules inside the cavities, have different terms: inside the open cavities of the polymer, or inside the cavities formed by packing different polymers. The host backbone shows responsive dynamic behavior in order to accommodate the size and shape of incoming guest molecule or guest aggregates. Simulations show that the host-guest bi...

  19. 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.

  20. Water-soluble vitamins.

    Science.gov (United States)

    Konings, Erik J M

    2006-01-01

    Simultaneous Determination of Vitamins.--Klejdus et al. described a simultaneous determination of 10 water- and 10 fat-soluble vitamins in pharmaceutical preparations by liquid chromatography-diode-array detection (LC-DAD). A combined isocratic and linear gradient allowed separation of vitamins in 3 distinct groups: polar, low-polar, and nonpolar. The method was applied to pharmaceutical preparations, fortified powdered drinks, and food samples, for which results were in good agreement with values claimed. Heudi et al. described a separation of 9 water-soluble vitamins by LC-UV. The method was applied for the quantification of vitamins in polyvitaminated premixes used for the fortification of infant nutrition products. The repeatability of the method was evaluated at different concentration levels and coefficients of variation were principle in a specific and sensitive method for the determination of free and bound pantothenic acid in a large variety of foods. A French laboratory invited European laboratories to participate in a series of collaborative studies for this method, which will be carried out in 2005/2006. A more sophisticated method was described by Mittermayer et al. They developed an LC-mass spectrometry (LC/MS) method for the determination of vitamin B5 in a wide range of fortified food products. Application of the method to various samples showed consistent results with those obtained by microbiology. Vitamin B6.-Method 2004.07, an LC method for the analysis of vitamin B6 in reconstituted infant formula, was published by Mann et al. In contrast with this method, which quantifies vitamin B6 after converting the phosphorylated and free vitamers into pyridoxine, Viñas et al. published an LC method which determines 6 vitamin B6 related compounds, the 3 B6 vitamers, their corresponding phosphorylated esters, and a metabolite. Accuracy was determined using 2 CRMs. Results were within the certified ranges. Vitamin C.-Franke et al. described an extensive

  1. Conjugated polymer fluorescence: Interplay of correlations and alternation

    Energy Technology Data Exchange (ETDEWEB)

    Soos, Z.G. [Princeton Univ., NJ (United States). Dept. of Chemistry; Galvao, D.S. [Bell Communications Research, Inc., Red Bank, NJ (United States)]|[Universidade Estadual de Campinas, SP (Brazil). Dept. de Fisica Aplicada; Etemad, S. [Bell Communications Research, Inc., Red Bank, NJ (United States); Kepler, R.G. [Sandia National Labs., Albuquerque, NM (United States)

    1993-12-31

    Conjugated polymers can have high conductivity on doping, large nonlinear optical response in semiconducting state, and be used as LEDs. These polymers include polyactylene, polydiacetylenes, polysilanes, polythiophene, poly-p-phenylenevinylene. Polymer fluorescence is related to the lowest singlet excited state S{sub 1}. Polymer and oligomer data are shown for the excitation energy ratio of the two-photon and one-photon gaps. There is a ratio crossover with increasing e-e correlations in any centrosymmetri chain with an insulating ground state. The {pi}-conjugated polymers present various band gaps at constant correlations, and single-particle gaps can be related to the structure. The nature of the lowest singlet excited state depends sensitively on both correlations and alternation. 22 refs, 2 figs.

  2. Naphthobischalcogenadiazole Conjugated Polymers: Emerging Materials for Organic Electronics.

    Science.gov (United States)

    Osaka, Itaru; Takimiya, Kazuo

    2017-07-01

    π-Conjugated polymers are an important class of materials for organic electronics. In the past decade, numerous polymers with donor-acceptor molecular structures have been developed and used as the active materials for organic devices, such as organic field-effect transistors (OFETs) and organic photovoltaics (OPVs). The choice of the building unit is the primary step for designing the polymers. Benzochalcogenadiazoles (BXzs) are one of the most familiar acceptor building units studied in this area. As their doubly fused system, naphthobischalcogenadiazoles (NXzs), i.e., naphthobisthiadiazole (NTz), naphthobisoxadiazole (NOz), and naphthobisselenadiazole (NSz) are emerging building units that provide interesting electronic properties and highly self-assembling nature for π-conjugated polymers. With these fruitful features, π-conjugated polymers based on these building units demonstrate great performances in OFETs and OPVs. In particular, in OPVs, NTz-based polymers have exhibited more than 10% efficiency, which is among the highest values reported so far. In this Progress Report, the synthesis, properties, and structures of NXzs and their polymers is summarized. The device performance is also highlighted and the structure-property relationships of the polymers are discussed. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. Structure and Conformation of Ionic Conjugated Polymers: Polydots

    Science.gov (United States)

    Osti, Naresh; Etampawala, Thusitha; Wijesinghe, Sidath; Perahia, Dvora

    2014-03-01

    Conjugated polymers confining into nano dimension form long-lived highly luminescent tunable organic particles of having enormous potential for intracellular imaging and drug delivery. Even though the chains are not in their thermodynamically stable conformation, the poly-dots remain stable over long period of times. Incorporation of ionic groups into conjugated polymers introduces a configuration control factor that impacts their conformation and their applications as luminescent probes. The current work investigates the structure and stability of poly-dots of di-alkoxy para polyphenyleneethynylene (PPE) conjugated polymer substituted with carboxylate side chain. Our small angle neutron scattering (SANS) studies have shown that ionic PPE forms spherical poly-dots in water. Ionic Poly-dots remain stable up to a temperature of 800C compare to neutral conjugated polymer poly dots. These polymer dots were allowed to assemble at a solid surface and observed by AFM which showed the nano aggregates of different sizes that assembled in different ways depending on the concentration and molecular parameters of the ionic PPEs used.

  4. 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.

  5. Highly Active Water-Soluble Olefin Metathesis Catalyst

    OpenAIRE

    Hong, Soon Hyeok; Grubbs, Robert H

    2006-01-01

    A novel water-soluble ruthenium olefin metathesis catalyst supported by a poly(ethylene glycol) conjugated saturated 1,3-dimesityl-4,5-dihydroimidazol-2-ylidene ligand is reported. The catalyst displays improved activity in ring-opening metathesis polymerization, ring-closing metathesis, and cross-metathesis reactions in aqueous media.

  6. Enhanced photoluminescence of conjugated polymer thin films on nanostructured silver

    Energy Technology Data Exchange (ETDEWEB)

    Griffo, Michael S., E-mail: mgriffo@physics.ucsc.edu [Physics Department, University of California, Santa Cruz, 1156 High Street, Santa Cruz, CA 95064 (United States); Carter, Sue A., E-mail: sacarter@ucsc.edu [Physics Department, University of California, Santa Cruz, 1156 High Street, Santa Cruz, CA 95064 (United States); Holt, Amanda L. [Collaborative Biotechnologies, University of California, Santa Barbara, Marine Biotechnology Building, Santa Barbara, CA 93106 (United States)

    2011-08-15

    Photoluminescence of a conjugated polymer in the presence of surface plasmons on metallic nanoparticles is studied. A layered device structure was constructed that enabled control over nanoparticle diameter and separation between the polymer and nanoparticles layers. The dependence of the surface plasmon evanescent field and energy transfer has been investigated with the largest enhancement in photoluminescence observed at a 40 nm distance separation between the fluorophore and the surface plasmon. A spectrum of surface plasmon resonances ranging from the emission to the absorption energies of the conjugated polymer revealed largest enhancements when the resonance was tuned to the conjugated polymer emission energy. At peak photoluminescence the maximum photoluminescent enhancement was found to be 5.6 times of the photoluminescence of the control structure and the total integrated enhancement was 5.9 times. - Highlights: > Change in photoluminescence (PL) of a polymer on a nanostructured metal surface is studied. > Largest increase in PL occurs at 40 nm distance, 10x larger than for small molecules, due to stronger quenching. > At peak, 5.6 time enhancement in the PL efficiency is observed.

  7. Composites based on cellulose fiber nonwovens and a water soluble polymer 1. Structure and strength-deformation characteristics of cellulose fiber nonwovens and structural characteristics of the composites

    Science.gov (United States)

    Cerpakovska, D.; Kalnins, M.

    2012-03-01

    The results of a study on the strength-deformation characteristics (tensile elastic modulus, ultimate strength, elongation at break, and punching and tearing strengths) of two kinds of cellulose fiber nonwovens (CFNs) with dissimilar void content and different geometrical parameters of cellulose fibers are discussed. The structural characteristics of composites prepared by impregnation with poly(vinyl alcohol) water solutions are analyzed, too. Composites with volume fractions of polymer up to 0.4% and volume fractions of voids up to 0.3% were prepared. Filling of voids by the polymer occurred without significant changes in the structure of CFNs. The fraction of closed voids increased with polymer content.

  8. Recent Advances in Polymer Organic Light-Emitting Diodes (PLED) Using Non-conjugated Polymers as the Emitting Layer and Contrasting Them with Conjugated Counterparts

    Science.gov (United States)

    Wong, Michael Y.

    2017-11-01

    Polymer organic light-emitting diodes (PLED) are one of the most studied subjects in flexible electronics thanks to their economical wet fabrication procedure for enhanced price advantage of the product device. In order to optimize PLED efficiency, correlating the polymer structure with the device performance is essential. An important question for the researchers in this field is whether the polymer backbone is conjugated or not as it affects the device performance. In this review, recent advances in non-conjugated polymers employed as the emitting layer in PLED devices are first discussed, followed by their contrast with the conjugated counterparts in terms of polymer synthesis, sample quality, physical properties and device performances. Such comparison between conjugated and non-conjugated polymers for PLED applications is rarely attempted, and; hence, this review shall provide a useful insight of emitting polymers employed in PLEDs.

  9. Dithienocarbazole and isoindigo based amorphous low bandgap conjugated polymers for efficient polymer solar cells.

    Science.gov (United States)

    Deng, Yunfeng; Liu, Jian; Wang, Jiantai; Liu, Lihui; Li, Weili; Tian, Hongkun; Zhang, Xiaojie; Xie, Zhiyuan; Geng, Yanhou; Wang, Fosong

    2014-01-22

    Three highly rigid and planar low-bandgap conjugated polymers comprising alternate isoindigo and dithienocarbazole groups are synthesized for the fabrication of high performance polymer solar cells. Power conversion efficiencies of up to 7.2% for conventional devices and 8.2% for inverted devices are demonstrated. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. 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

    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....... 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......-green emission and the zinc-porphyrin linked homopolymers emit near-infrared/infrared light. This was demonstrated to be due to electroluminescence pumping of the zinc-porphyrin moieties that were covalently linked to homopolymer material. When only one zinc-porphyrin dye was incorporated into the backbone...

  11. Magnetism in Pristine Pi-conjugated Polymers

    Science.gov (United States)

    2014-09-07

    characterisation of macrocyclic oligothiophenes. As a general approach to the synthesis of macrocycles chain ends of oligomers and polymers were brominated (α...alkylthiophenes) on their magnetic properties and the results obtained for the magnetic properties of gold nanoparticles . This strongly supported

  12. Network formation mechanisms in conjugated microporous polymers

    OpenAIRE

    Laybourn, Andrea; Dawson, Robert; Clowes, Rob; Hasell, Tom; Cooper, Andrew I.; Khimyak, Yaroslav Z.; Adams, Dave J.

    2014-01-01

    We discuss in detail the mechanism of formation of a highly microporous polymer, CMP-1, formed mainly via Sonogashira–Hagihara coupling. We demonstrate how the microporosity evolves with time, and discuss the importance of alkyne homo-coupling on the microporosity.

  13. Self-assembly of conjugated polymer-Ag@SiO2 hybrid fluorescent nanoparticles for application to cellular imaging.

    Science.gov (United States)

    Tang, Fu; He, Fang; Cheng, Huicong; Li, Lidong

    2010-07-20

    A novel fluorescent nanoparticle was prepared via a simple self-assembly technique based on water-soluble conjugated polymers (CPs) and Ag@SiO(2) core-shell nanoparticles. Core-shell nanoparticles with silver NPs core show a unique property referred to as metal-enhanced fluorescence (MEF). In the present work, the cationic conjugated polymer poly[9,9'-bis(6''-(N,N,N-trimethylammonium)-hexyl) fluorene-2,7-ylenevinylene-co-alt-1,4-phenylene dibromide] (PFV) was hybridized with Ag@SiO(2) NPs via simple self-assembly procedure, and given high stability, monodispersity. The fluorescence intensity of PFV after assembling on Ag@SiO(2) core-shell NPs is enhanced 1.3-fold compared with the fluorescence intensity of PFV assembled on silica NPs without silver cores for the MEF property of the Ag@SiO(2) nanostructure. Nanocomposite with bright fluorescence was obtained. Moreover, the nanocomposition exhibits good monodispersity and low cytotoxicity, which promote their application in cellular imaging. Furthermore, fluorescent nanoparticles with amendable peripheral surfaces can also be potentially obtained because of the easy modification property of CPs and give potential application in selective biological sensing and imaging.

  14. Designing dapsone polymer conjugates for controlled drug delivery.

    Science.gov (United States)

    Rojo, Luis; Fernandez-Gutierrez, Mar; Deb, Sanjukta; Stevens, Molly M; San Roman, Julio

    2015-11-01

    Polymer-drug conjugates have significantly influenced polymer therapeutics over the last decade via controlled pharmacokinetics. Dapsone (4,4'-diamino diphenylsulphone) is not only widely used in the treatment of leprosy but forms an essential component in the treatment of autoimmune inflammatory diseases and malaria. However, its low bioavailability and non-specific distribution in the body leads to absorption throughout organs including skin, liver, and kidneys that can cause serious side effects. Thus, in this study we report the synthesis of polymer-drug conjugates of dapsone covalently bonded to macromolecular chains towards the development of new bioactive polymeric formulations with anti-inflammatory properties. Dapsone was functionalised with an acrylic moiety in which the acrylamide residue was directly bonded to one of the aromatic rings of dapsone. This functionalisation yielded an unsymmetrical dapsone methacrylamide (DapMA) structure, which on free radical polymerisation and co-polymerisation with HEMA yielded polymers of hydrocarbon macromolecules with pendant dapsone units. Thermal and size-exclusion chromatographic analysis revealed an increase in thermal stabilisation of the homopolymer (p(DapMA)) in comparison to the copolymer (p(Dap-co-HEMA)) with relatively high average molecular weight. The polymer conjugates exhibited high stability with low dapsone release from the polymeric backbone due to hydrolysis. However, a significant anti-inflammatory activity in a nitric oxide inhibition assay confirmed that this property was the consequence of only the macromolecular composition and not related to the release of low molecular weight compounds. Thus, the conjugation of dapsone to macromolecular systems provides a synthetic route to incorporate this drug into polymeric systems, facilitating their development into new anti-inflammatory therapies. The dapsone-conjugated methacrylic monomer and polymer derivatives with anti-inflammatory properties

  15. 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.

  16. Statistical conjugated polymers comprising optoelectronically distinct units.

    Science.gov (United States)

    Hollinger, Jon; Sun, Jing; Gao, Dong; Karl, Dominik; Seferos, Dwight S

    2013-03-12

    Poly(3-heptylselenophene)-stat-poly(3-hexylthiophene) is synthesized and characterized in terms of its crystallinity and performance in an organic photovoltaic (OPV) cell. Despite the random distribution of units along the polymer main chain, the material is semi-crystalline, as demonstrated by differential scanning calorimetry and wide-angle X-ray diffraction. Thin-film absorption suggests an increased compatibility than seen with 3-hexylselenophene monomer. Optoelectronic properties are an average of the two homopolymers, and OPV performance is enhanced by a broadened absorption profile and a favorable morphology. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. Water-Soluble Nanodiamond (Postprint)

    Science.gov (United States)

    2012-03-01

    nanodiamond salt that reacts with either alkyl or aryl halides by electron transfer to yield radical anions that dissociate spontaneously into free radicals...sodium in liquid ammonia leads to the nanodiamond salt 1. This material can be reacted with either alkyl or aryl halides to yield a radical anion that...From - To) March 2012 Technical Paper 1 October 2008 – 1 March 2012 4. TITLE AND SUBTITLE WATER-SOLUBLE NANODIAMOND (POSTPRINT) 5a. CONTRACT

  18. Direct (Hetero)arylation Polymerization: Simplicity for Conjugated Polymer Synthesis.

    Science.gov (United States)

    Pouliot, Jean-Rémi; Grenier, François; Blaskovits, J Terence; Beaupré, Serge; Leclerc, Mario

    2016-11-23

    Direct (hetero)arylation polymerization (DHAP) has recently been established as an environmentally benign method for the preparation of conjugated polymers. This synthetic tool features the formation of C-C bonds between halogenated (hetero)arenes and simple (hetero)arenes with active C-H bonds, thereby circumventing the preparation of organometallic derivatives and decreasing the overall production cost of conjugated polymers. Since its inception, selectivity and reactivity of DHAP procedures have been improved tremendously through the careful scrutinity of polymerization outcomes and the fine-tuning of reaction conditions. A broad range of monomers, from simple arenes to complex functionalized heteroarenes, can now be readily polymerized. The successful application of DHAP now leads to nearly defect-free conjugated polymers possessing comparable, if not slightly better, characteristics than their counterparts prepared using classical cross-coupling methods. This comprehensive review describes the mechanisms involved in this process from experimental and theoretical standpoints, presents an up-to-date compendium of materials obtained by this means, and exposes its current limitations and challenges.

  19. 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...... 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....

  20. 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.

  1. The structure of polymer carriers controls the efficacy of the experimental combination treatment of tumors with HPMA copolymer conjugates carrying doxorubicin and docetaxel.

    Science.gov (United States)

    Šírová, Milada; Strohalm, Jiří; Chytil, Petr; Lidický, Ondřej; Tomala, Jakub; Říhová, Blanka; Etrych, Tomáš

    2017-01-28

    The tumor-specific targeting of cancerostatics using polymer drug carriers represents a potential strategy to achieve an effective treatment with reduced side toxicity. Synthetic water-soluble copolymers based on N-(2-hydroxypropyl)methacrylamide (HPMA) are carriers with tunable architecture and drug loading, tumor-specific accumulation of the drug, and its controlled release. We describe a combination treatment of murine EL4 T cell lymphoma with HPMA-based star conjugates (Mw 250,000gmol-1) of doxorubicin (Dox) or docetaxel (Dtx) designed for enhanced tumor accumulation and combination therapy. Although the combination of linear conjugates (Mw=28,000gmol-1) containing Dox or Dtx resulted in an additive effect in the treatment of the lymphoma, the opposite was observed in the combination of two star conjugates with Dox or Dtx, as the star Dtx conjugate decreased the treatment efficacy of the star Dox conjugate. The Dtx conjugate alone was virtually ineffective in the reduction of tumor growth or survival time extension; thus, a curative effect could be solely attributed to the Dox-containing conjugate. When Dtx was delivered to the tumor on the same polymer carrier as Dox, the efficacy of the Dox-induced treatment was reduced to a lesser extent. No reduction was found when Dtx was delivered by a linear polymer or applied as a free drug. The phenomenon was strictly related to the enhanced permeability and retention (EPR) effect, as it was not observed in BCL1 leukemia, a model without EPR. The diminished treatment outcome in the combination therapy with the two star conjugates was underlined by the significantly decreased accumulation of Dox in the tumor. The use of the drug-free polymer carrier instead of the Dtx-containing star conjugate did not reduce the treatment efficacy of the Dox conjugate. Thus, the physicochemical characteristics of the polymer carrier designed for tumor-specific drug delivery systems control the activity of the respective drug, leading to

  2. Monodisperse magnetite (Fe3O4) nanoparticles modified with water soluble polymers for the diagnosis of breast cancer by MRI method

    Science.gov (United States)

    Rezayan, Ali Hossein; Mousavi, Majid; Kheirjou, Somayyeh; Amoabediny, Ghasem; Ardestani, Mehdi Shafiee; Mohammadnejad, Javad

    2016-12-01

    In this study, magnetic nanoparticles (MNPs) were synthesized via co-precipitation method. To enhance the biocompatibility and colloidal stability of the synthesized nanoparticles, they were modified with carboxyl functionalized PEG via dopamine (DPA) linker. Both modified and unmodified Fe3O4 nanoparticles exhibited super paramagnetic behavior (particle size below 20 nm). The saturation magnetization (Ms) of PEGdiacid-modified Fe3O4 was 45 emu/g, which was less than the unmodified Fe3O4 nanoparticles (70 emu/g). This difference indicated that PEGdiacid polymer was immobilized on the surface of Fe3O4 nanoparticles successfully. To evaluate the efficiency of the resulting nanoparticles as contrast agents for magnetic resonance imaging (MRI), different concentration of MNPs and different value of echo time TE were investigated. The results showed that by increasing the concentration of the nanoparticles, transverse relaxation time (T2) decreased, which subsequently resulted in MR signal enhancement. T2-weighted MR images of the different concentration of MNPs in different value of echo time TE indicated that MR signal intensity increased with increase in TE value up to 66 and then remained constant. The cytotoxicity effect of the modified and unmodified nanoparticles was evaluated in three different concentrations (12, 60 and 312 mg l-1) on MDA-MB-231 cancer cells for 24 and 48 h. In both tested time (24 and 48 h) for all three samples, the modified nanoparticles had long life time than unmodified nanoparticles. Cellular uptake of modified MNPs was 80% and reduced to 9% by the unmodified MNPs.

  3. Preparation of Composite Films of a Conjugated Polymer and C60NWs and Their Photovoltaic Application

    OpenAIRE

    Takatsugu Wakahara; Kun’ichi Miyazawa; Osamu Ito; Nobutaka Tanigaki

    2016-01-01

    Composite films of conjugated polymers, such as poly[2-methoxy-5-(3′,7′-dimethyloctyloxy)-1,4-phenylenevinylene] (MDMO-PPV) and poly(3-hexylthiophene) (P3HT), with C60 nanowhiskers (C60NWs) were prepared. The photoluminescence originating from the conjugated MDMO-PPV polymers was effectively quenched in the composite film, indicating a strong interaction between the conjugated polymer and C60NWs. The photovoltaic devices were fabricated using C60NW (conjugated polymer) composite films, result...

  4. Displacement of polarons by vibrational modes in doped conjugated polymers

    Science.gov (United States)

    Anderson, M.; Ramanan, C.; Fontanesi, C.; Frick, A.; Surana, S.; Cheyns, D.; Furno, M.; Keller, T.; Allard, S.; Scherf, U.; Beljonne, D.; D'Avino, G.; von Hauff, E.; Da Como, E.

    2017-10-01

    Organic pi-conjugated polymers are deemed to be soft materials with strong electron-phonon coupling, which results in the formation of polarons, i.e., charge carriers dressed by self-localized distortion of the nuclei. Universal signatures for polarons are optical resonances below the band gap and intense vibrational modes (IVMs), both found in the infrared (IR) spectral region. Here, we study p -doped conjugated homo- and copolymers by combining first-principles modelling and optical spectroscopy from the far-IR to the visible. Polaronic IVMs are found to feature absorption intensities comparable to purely electronic transitions and, most remarkably, show only loose resemblance to the Raman or IR-active modes of the neutral polymer. The IVM frequency is dramatically scaled down (up to 50%) compared to the backbone carbon-stretching modes in the pristine polymers. The very large intensity of IVMs is associated with displacement of the excess positive charge along the backbone driven by specific vibrational modes. We propose a quantitative picture for the identification of these polaron shifting modes that solely based on structural information, directly correlates with their IR intensity. This finding finally discloses the elusive microscopic mechanism behind the huge IR intensity of IVMs in doped polymeric semiconductors.

  5. Monodisperse magnetite (Fe{sub 3}O{sub 4}) nanoparticles modified with water soluble polymers for the diagnosis of breast cancer by MRI method

    Energy Technology Data Exchange (ETDEWEB)

    Rezayan, Ali Hossein, E-mail: ahrezayan@ut.ac.ir [Department of Life Science Engineering, Faculty of New Sciences and Technologies, University of Tehran, Tehran (Iran, Islamic Republic of); Mousavi, Majid [Department of Life Science Engineering, Faculty of New Sciences and Technologies, University of Tehran, Tehran (Iran, Islamic Republic of); Kheirjou, Somayyeh [Department of Chemistry, Sharif University of Technology, Tehran (Iran, Islamic Republic of); Amoabediny, Ghasem [School of Chemical Engineering, College of Engineering, University of Tehran, Tehran (Iran, Islamic Republic of); Ardestani, Mehdi Shafiee [Department of Pharmacy, Tehran University of Medical Sciences, Tehran (Iran, Islamic Republic of); Mohammadnejad, Javad [Department of Life Science Engineering, Faculty of New Sciences and Technologies, University of Tehran, Tehran (Iran, Islamic Republic of)

    2016-12-15

    In this study, magnetic nanoparticles (MNPs) were synthesized via co-precipitation method. To enhance the biocompatibility and colloidal stability of the synthesized nanoparticles, they were modified with carboxyl functionalized PEG via dopamine (DPA) linker. Both modified and unmodified Fe{sub 3}O{sub 4} nanoparticles exhibited super paramagnetic behavior (particle size below 20 nm). The saturation magnetization (Ms) of PEGdiacid-modified Fe{sub 3}O{sub 4} was 45 emu/g, which was less than the unmodified Fe{sub 3}O{sub 4} nanoparticles (70 emu/g). This difference indicated that PEGdiacid polymer was immobilized on the surface of Fe{sub 3}O{sub 4} nanoparticles successfully. To evaluate the efficiency of the resulting nanoparticles as contrast agents for magnetic resonance imaging (MRI), different concentration of MNPs and different value of echo time TE were investigated. The results showed that by increasing the concentration of the nanoparticles, transverse relaxation time (T{sub 2}) decreased, which subsequently resulted in MR signal enhancement. T{sub 2}-weighted MR images of the different concentration of MNPs in different value of echo time TE indicated that MR signal intensity increased with increase in TE value up to 66 and then remained constant. The cytotoxicity effect of the modified and unmodified nanoparticles was evaluated in three different concentrations (12, 60 and 312 mg l{sup −1}) on MDA-MB-231 cancer cells for 24 and 48 h. In both tested time (24 and 48 h) for all three samples, the modified nanoparticles had long life time than unmodified nanoparticles. Cellular uptake of modified MNPs was 80% and reduced to 9% by the unmodified MNPs. - Highlights: • Magnetic nanoparticles (MNPs) were synthesized via co-precipitation method. • MNPs were modified with carboxyl functionalized PEG via dopamine (DPA) linker. • Modified and unmodified Fe{sub 3}O{sub 4} nanoparticles exhibited super paramagnetic behavior. • T{sub 2} decrease as MNPs

  6. Thiophene in Conducting Polymers: Synthesis of Poly(thiophene)s and Other Conjugated Polymers Containing Thiophenes, for Application in Polymer Solar Cells

    DEFF Research Database (Denmark)

    Livi, Francesco; Carlé, Jon Eggert; Bundgaard, Eva

    2015-01-01

    Conducting polymers based on thiophene are described. The polymers include poly(thiophene) with and without side-chains and other conjugated polymers in general, based on thiophene. The synthesis and characteristics of the polymers are described along with the application of these as light......-absorbing materials in polymer solar cells....

  7. 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.

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

    Science.gov (United States)

    Piwoński, Hubert; Michinobu, Tsuyoshi; Habuchi, Satoshi

    2017-05-01

    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.

  9. Conjugated polymer light-emitting diodes: Synthesis, fabrication and characterization

    Science.gov (United States)

    Kasim, Ramesh Kumar

    A new conjugated polymer, poly(2,6-quinoline vinylene) was synthesized by direct polymerization and via a precursor route. The optical band gap of the polymer was determined to be 2.39 eV. Precursor polymer, with xanthate as the leaving group, was prepared and electroluminescent properties of the con ugated polymer were characterized. A copolymer namely, poly(1,4-phenylene vinylene-co-2,6-quinoline vinylene), PPVQV, containing p-type and n-type segments, was prepared via a precursor route and characterized. The EL spectrum of the copolymer is blue shifted with respect to both PPV and PQV. Bilayer devices with PPV and PPVQV yielded improved emission efficiency. Further improvement in emission efficiency was achieved by using blends of copolymer and PPV homopolymer to construct devices with 'graded' composition. EL properties of poly(4,4'-dinonyl-2,2' -bithiazol-5,5'-diyl) (PNBT) and its methylated derivative (MPNBT) were characterized. PNBT showed orange emission and intensity decreased very rapidly. Continued operation at higher voltages caused a red shift in the emission spectrum. MPNBT showed orange EL with broader emission spectrum. Bilayer and blend devices consisting of MPNBT and PPV showed lower onset field. EL properties of electron withdrawing group substituted thiophene-based polymers with regioregular and regiorandom structures were characterized. Regioregular polymers showed lower EL efficiency than respective regiorandom polymers. A non-catalytic chemical reduction method to deposit silver on polymer films was developed. It yielded shiny films with good polymer/metal interface. The deposition was carried out on a lab bench without special precautions. Strong reduction conditions gave gray or brown spongy films, while mild reduction conditions yielded good quality films. LEDs that work under both forward and reverse dc bias were fabricated using PPV as emission layer. The reverse bias EL in LEDs on heat-treated ITO substrates is attributed to the

  10. 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

    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...... 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....

  11. Solvent immersion nanoimprint lithography of fluorescent conjugated polymers

    Energy Technology Data Exchange (ETDEWEB)

    Whitworth, G. L.; Zhang, S.; Stevenson, J. R. Y.; Ebenhoch, B.; Samuel, I. D. W.; Turnbull, G. A. [Organic Semiconductor Centre, SUPA, School of Physics and Astronomy, University of St Andrews, St Andrews KY16 9SS (United Kingdom)

    2015-10-19

    Solvent immersion imprint lithography (SIIL) was used to directly nanostructure conjugated polymer films. The technique was used to create light-emitting diffractive optical elements and organic semiconductor lasers. Gratings with lateral features as small as 70 nm and depths of ∼25 nm were achieved in poly(9,9-dioctylfluorenyl-2,7-diyl). The angular emission from the patterned films was studied, comparing measurement to theoretical predictions. Organic distributed feedback lasers fabricated with SIIL exhibited thresholds for lasing of ∼40 kW/cm{sup 2}, similar to those made with established nanoimprint processes. The results show that SIIL is a quick, convenient and practical technique for nanopatterning of polymer photonic devices.

  12. Silica passivated conjugated polymer nanoparticles for biological imaging applications

    Science.gov (United States)

    Bourke, Struan; Urbano, Laura; Olona, Antoni; Valderrama, Ferran; Dailey, Lea Ann; Green, Mark A.

    2017-02-01

    Colorectal and prostate cancers are major causes of cancer-related death, with early detection key to increased survival. However, as symptoms occur during advanced stages and current diagnostic methods have limitations, there is a need for new fluorescent probes that remain bright, are biocompatible and can be targeted. Conjugated polymer nanoparticles have shown great promise in biological imaging due to their unique optical properties. We have synthesised small, bright, photo-stable CN-PPV, nanoparticles encapsulated with poloxamer polymer and a thin silica shell. By incubating the CN-PPV silica shelled cross-linked (SSCL) nanoparticles in mammalian (HeLa) cells; we were able to show that cellular uptake occurred. Uptake was also shown by incubating the nanoparticles in RWPE-1, WPE1-NB26 and WPE1- NA22 prostate cancer cell lines. Finally, HEK cells were used to show the particles had limited cytotoxicity.

  13. Crystallization-driven assembly of conjugated-polymer-based nanostructures

    Energy Technology Data Exchange (ETDEWEB)

    Hayward, Ryan C. [Univ. of Massachusetts, Amherst, MA (United States). Polymer Science & Engineering

    2016-10-15

    The goal of this project has been to improve our ability to simultaneously control the organization, and therefore the opto-electronic properties, of conjugated-polymer based materials across three different length-scales: 1) the molecular scale, in the sense of controlling growth and functionalization of highly crystalline semiconducting organic materials capable of efficient charge transport, 2) the nanoscale, in terms of positioning n- and p-type materials with domain sizes comparable to exciton diffusion lengths (~ 10 nm) to facilitate charge separation, and 3) the colloidal scale, such that well-defined crystalline nanoscale building blocks can be hierarchically organized into device layers. As described in more detail below, the project was successful in generating powerful new approaches to, and improved fundamental understanding of, processing and self-assembly of organic and hybrid semiconducting materials across all three length-scales. Although the goals of the project were formulated with primarily photovoltaic architectures in mind, the outcomes of the project have significant implications for a variety of conjugated-polymer-based devices including field-effect-transistors for sensors and logic devices, as well as potentially thermoelectrics and battery electrode materials. The project has resulted in 10 peer-reviewed publications to date [1-10], with several additional manuscripts currently in preparation.

  14. Recent Advances in Conjugated Polymer-Based Microwave Absorbing Materials

    Directory of Open Access Journals (Sweden)

    Ying Wang

    2017-01-01

    Full Text Available Microwave absorbing materials (MAMs are paving the way for exciting applications in electromagnetic (EM pollution precaution and national defense security, as they offer an advanced alternative to conventional reflection principles to fundamentally eliminate the EM waves. Conjugated polymer (CP-based composites appear as a promising kind of MAM with the desirable features of low density and high performance. In this review, we introduce the theory of microwave absorption and summarize recent advances in the fabrication of CP-based MAMs, including rational design of the microstructure of pure conjugated polymers and tunable chemical integration with magnetic ferrites, magnetic metals, transition metal oxides, and carbon materials. The key point of enhancing microwave absorption in CP-based MAMs is to regulate their EM properties, improve matching of characteristic impedance, and create diversified loss mechanisms. The examples presented in this review will provide new insights into the design and preparation of CP-based composites that can satisfy the high demands of the oncoming generation of MAMs.

  15. 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.

  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: Physical chemistry Impact factor: 6.459, year: 2016

  17. Novel conjugates of peptides and conjugated polymers for optoelectronics and neural interfaces

    Science.gov (United States)

    Bhagwat, Nandita

    Peptide-polymer conjugates are a novel class of hybrid materials that take advantage of each individual component giving the opportunity to generate materials with unique physical, chemical, mechanical, optical, and electronic properties. In this dissertation peptide-polymer conjugates for two different applications are discussed. The first set of peptide-polymer conjugates were developed as templates to study the intermolecular interactions between electroactive molecules by manipulating the intermolecular distances at nano-scale level. A PEGylated, alpha-helical peptide template was employed to effectively display an array of organic chromophores (oxadiazole containing phenylenevinylene oligomers, Oxa-PPV). Three Oxa-PPV chromophores were strategically positioned on each template, at distances ranging from 6 to 17 A from each other, as dictated by the chemical and structural properties of the peptide. The Oxa-PPV modified PEGylated helical peptides (produced via Heck coupling strategies) were characterized by a variety of spectroscopic methods. Electronic contributions from multiple pairs of chromophores on a scaffold were detectable; the number and relative positioning of the chromophores dictated the absorbance and emission maxima, thus confirming the utility of these polymer--peptide templates for complex presentation of organic chromophores. The rest of the thesis is focused on using poly(3,4-alkylenedioxythiophene) based conjugated polymers as coatings for neural electrodes. This thiophene derivative is of considerable current interest for functionalizing the surfaces of a wide variety of devices including implantable biomedical electronics, specifically neural bio-electrodes. Toward these ends, copolymer films of 3,4-ethylenedioxythiophene (EDOT) with a carboxylic acid functional EDOT (EDOTacid) were electrochemically deposited and characterized as a systematic function of the EDOTacid content (0, 25, 50, 75, and 100%). The chemical surface characterization

  18. Molecular structure and exciton dynamics in organic conjugated polymers

    Science.gov (United States)

    Thomas, Alan K.

    Intermolecular electronic interactions, dipole coupling and orbital overlap, caused by pi-pi stacking in organic conjugated polymers lead to unique structures and properties that can be harnessed for optoelectronic applications. These interactions define structure-function relationships in amorphous and aggregated forms of polymers in the solid state and determine their efficiencies and functionality in electronic devices, from transistors to solar cells. Organic polymer electronic device performance depends critically upon electronic coupling between monomer units -mediated by conformation and packing characteristics - that dictates electronic properties like conductivity and capacitance as well as electronic processes, such as charge carrier generation and transport. This dissertation demonstrates how electronic processes in conjugated polymers are mediated by subtle inter- and intra-chain electronic interactions imparted by the conformational degrees of freedom within their solid state structure and how this effects device performance. To initiate this investigation into structure-function relationships, an examination of nanoparticles representing two limiting aggregation states of the conjugated polymer poly(3-hexylthiophene) (P3HT) was conducted. These aggregates are defined by their predominate form of electronic coupling, inter- or intrachain, called H- and J-aggregates respectively. H- or J-aggregates of P3HT were embedded in an insulating matrix and time-resolved fluorescence intensity modulation spectroscopy was utilized to uncover the existence of efficient singlet-triplet quenching in J aggregates not present in H-aggregates. These studies were extended by examining P3HT H-and J-aggregates under applied electric fields in capacitor type devices using multiple time-resolved and steady-state spectroscopic techniques. These experiments reveal electronic couplings in J aggregates that shift excited state population towards a majority composed of long lived

  19. Surface doping of conjugated polymers by graphene oxide and its application for organic electronic devices

    Energy Technology Data Exchange (ETDEWEB)

    Gao, Yan [Department of Materials Science and Engineering, University of Washington, Box 352120, Seattle, WA 98195 (United States); State Key Laboratory of Silicon Materials, MOE Key Laboratory of Macromolecule Synthesis and Functionalization, Zhejiang-California International Nanosystems Institute, Zhejiang University, Hangzhou 310027 (China); Yip, Hin-Lap; Chen, Kung-Shih; Acton, Orb; Sun, Ying [Department of Materials Science and Engineering, University of Washington, Box 352120, Seattle, WA 98195 (United States); O' Malley, Kevin M.; Ting, Guy [Department of Chemistry, University of Washington, Box 351700, Seattle, WA 98195 (United States); Chen, Hongzheng [State Key Laboratory of Silicon Materials, MOE Key Laboratory of Macromolecule Synthesis and Functionalization, Zhejiang-California International Nanosystems Institute, Zhejiang University, Hangzhou 310027 (China); Jen, Alex K.Y. [Department of Materials Science and Engineering, University of Washington, Box 352120, Seattle, WA 98195 (United States); Department of Chemistry, University of Washington, Box 351700, Seattle, WA 98195 (United States)

    2011-04-26

    Surface doping of conjugated polymers is realized by depositing a thin layer of graphene oxide (GO) on top of the polymers. The high proton density and the unique 2D structure of GO facilitate the protonic surface doping of conjugated polymers to achieve high conductivities. This finding represents a new strategy for improving charge transport across the metal/conjugated polymer interface to achieve much improved performance in organic solar cells. (Copyright copyright 2011 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  20. Manipulating Energy Transfer in Conjugated Polymers using Radical Mediators

    Science.gov (United States)

    Wilcox, Daniel; Mukherjee, Sanjoy; Boudouris, Bryan

    Previous efforts have demonstrated that polymers containing open-shell moieties can be used to improve the performance of organic electronic devices (e.g., organic field-effect transistors (OFETs) and photovoltaic devices). However, the exact mechanism of how these redox-active radical polymers improve the performance of these next-generation devices has yet to be described in full. Here, we take the first steps towards elucidating this full picture by demonstrating that the galvinoxyl radical can be used as an electron acceptor for a common electron-donating macromolecule. First, galvinoxyl was used as a fluorescence quencher for poly(3-hexylthiophene) (P3HT) with quenching performance on par with that of oft-used fullerene derivatives. This effect was caused by photoinduced electron transfer between the two materials. Additionally, the galvinoxyl radical was used as an active layer dopant for P3HT OFETs. By increasing the P3HT carrier density through spontaneous electron transfer, the behavior of the device was changed from that of an intrinsic semiconductor to that of a highly-doped semiconductor. Thus, these initial studies lay the foundation for a paradigm where open-shell entities are used to dope conjugated polymer semiconductors for high-performance device applications.

  1. Parallel Synthesis of photoluminescent π-conjugated polymers by polymer reactions of an organotitanium polymer with a titanacyclopentadiene unit.

    Science.gov (United States)

    Matsumura, Yoshimasa; Fukuda, Katsura; Inagi, Shinsuke; Tomita, Ikuyoshi

    2015-04-01

    A regioregular organometallic polymer with titanacyclopentadiene unit, obtained by the reaction of a 2,7-diethynylfluorene derivative and a low-valent titanium complex, is subjected to the reaction with three kinds of electrophiles (i.e., sulfur monochloride, hydrochloric acid, and dichlorophenylphosphine) to give π-conjugated polymers possessing both fluorene and building blocks originated from the transformation of the titanacycles in the main chain. For example, a phosphole-containing polymer whose number-average molecular weight is estimated as 5000 is obtained in 50% yield. The obtained thiophene, butadiene, and phosphole-containing polymers exhibit efficient photoluminescence (PL) with emission colors of blue, green, and yellow, respectively. For example, the phosphole-containing polymer exhibits yellow PL with an emission maximum (Emax ) of 533 nm and a quantum yield (Φ) of 0.37. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. Structure and Morphology Control in Thin Films of Conjugated Polymers for an Improved Charge Transport

    OpenAIRE

    Haiyang Wang; Yaozhuo Xu; Xinhong Yu; Rubo Xing; Jiangang Liu; Yanchun Han

    2013-01-01

    The morphological and structural features of the conjugated polymer films play an important role in the charge transport and the final performance of organic optoelectronics devices [such as organic thin-film transistor (OTFT) and organic photovoltaic cell (OPV), etc.] in terms of crystallinity, packing of polymer chains and connection between crystal domains. This review will discuss how the conjugated polymer solidify into, for instance, thin-film structures, and how to control the molecula...

  3. Perspective: Optical spectroscopy in π-conjugated polymers and how it can be used to determine multiscale polymer structures

    Science.gov (United States)

    Barford, William; Marcus, Max

    2017-04-01

    Exciton delocalization in conjugated polymer systems is determined by polymer conformations and packing. Since exciton delocalization determines the photoluminescent vibronic progression, optical spectroscopy provides an indirect link to polymer multiscale structures. This perspective describes our current theoretical understanding of how exciton delocalization in π-conjugated polymers determines their optical spectroscopy and further shows how exciton delocalization is related to conformational and environmental disorder. If the multiscale structures in conjugated polymer systems are known, then using first-principles modeling of excitonic processes it is possible to predict a wide-range of spectroscopic observables. We propose a reverse-engineering protocol of using these experimental observables in combination with theoretical and computational modeling to determine the multiscale polymers structures, thus establishing quantitative structure-function predictions.

  4. Conjugated Polymer Zwitterions: Efficient Interlayer Materials in Organic Electronics.

    Science.gov (United States)

    Liu, Yao; Duzhko, Volodimyr V; Page, Zachariah A; Emrick, Todd; Russell, Thomas P

    2016-11-15

    Conjugated polymer zwitterions (CPZs) are neutral, hydrophilic, polymer semiconductors. The pendent zwitterions, viewed as side chain dipoles, impart solubility in polar solvents for solution processing, and open opportunities as interfacial components of optoelectronic devices, for example, between metal electrodes and organic semiconductor active layers. Such interlayers are crucial for defining the performance of organic electronic devices, e.g., field-effect transistors (OFETs), light-emitting diodes (OLEDs), and photovoltaics (OPVs), all of which consist of multilayer structures. The interlayers reduce the Schottky barrier height and thus improve charge injection in OFETs and OLEDs. In OPVs, the interlayers serve to increase the built-in electric potential difference (Vbi) across the active layer, ensuring efficient extraction of photogenerated charge carriers. In general, polar and even charged electronically active polymers have gained recognition for their ability to modify metal/semiconductor interfaces to the benefit of organic electronics. While conjugated polyelectrolytes (CPEs) as interlayer materials are well-documented, open questions remain about the role of mobile counterions in CPE-containing devices. CPZs possess the processing advantages of CPEs, but as neutral molecules lack any potential complications associated with counterions. The electronic implications of CPZs on metal electrodes stem from the orientation of the zwitterion dipole moment in close proximity to the metal surface, and the resultant surface-induced polarization. This generates an interfacial dipole (Δ) at the CPZ/metal interface, altering the work function of the electrode, as confirmed by ultraviolet photoelectron spectroscopy (UPS), and improving device performance. An ideal cathode interlayer would reduce electrode work function, have orthogonal processability to the active layer, exhibit good film forming properties (i.e., wettability/uniformity), prevent exciton

  5. 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.

  6. Understanding the Structural Evolution of Single Conjugated Polymer Chain Conformers

    Directory of Open Access Journals (Sweden)

    Adam J. Wise

    2016-11-01

    Full Text Available Single molecule photoluminescence (PL spectroscopy of conjugated polymers has shed new light on the complex structure–function relationships of these materials. Although extensive work has been carried out using polarization and excitation intensity modulated experiments to elucidate conformation-dependent photophysics, surprisingly little attention has been given to information contained in the PL spectral line shapes. We investigate single molecule PL spectra of the prototypical conjugated polymer poly[2-methoxy-5-(2-ethylhexyloxy-1,4-phenylenevinylene] (MEH-PPV which exists in at least two emissive conformers and can only be observed at dilute levels. Using a model based on the well-known “Missing Mode Effect” (MIME, we show that vibronic progression intervals for MEH-PPV conformers can be explained by relative contributions from particular skeletal vibrational modes. Here, observed progression intervals do not match any ground state Raman active vibrational frequency and instead represent a coalescence of multiple modes in the frequency domain. For example, the higher energy emitting “blue” MEH-PPV form exhibits PL maxima at ~18,200 cm−1 with characteristic MIME progression intervals of ~1200–1350 cm−1, whereas the lower energy emitting “red” form peaks at ~17,100 cm−1 with intervals in the range of ~1350–1450 cm−1. The main differences in blue and red MEH-PPV chromophores lie in the intra-chain order, or, planarity of monomers within a chromophore segment. We demonstrate that the Raman-active out-of-plane C–H wag of the MEH-PPV vinylene group (~966 cm−1 has the greatest influence in determining the observed vibronic progression MIME interval. Namely, larger displacements (intensities—indicating lower intra-chain order—lower the effective MIME interval. This simple model provides useful insights into the conformational characteristics of the heterogeneous chromophore landscape without requiring costly and

  7. Design of Stomach Acid-Stable and Mucin-Binding Enzyme Polymer Conjugates.

    Science.gov (United States)

    Cummings, Chad S; Campbell, Alan S; Baker, Stefanie L; Carmali, Sheiliza; Murata, Hironobu; Russell, Alan J

    2017-02-13

    The reduced immunogenicity and increased stability of protein-polymer conjugates has made their use in therapeutic applications particularly attractive. However, the physicochemical interactions between polymer and protein, as well as the effect of this interaction on protein activity and stability, are still not fully understood. In this work, polymer-based protein engineering was used to examine the role of polymer physicochemical properties on the activity and stability of the chymotrypsin-polymer conjugates and their degree of binding to intestinal mucin. Four different chymotrypsin-polymer conjugates, each with the same polymer density, were synthesized using "grafting-from" atom transfer radical polymerization. The influence of polymer charge on chymotrypsin-polymer conjugate mucin binding, bioactivity, and stability in stomach acid was determined. Cationic polymers covalently attached to chymotrypsin showed high mucin binding, while zwitterionic, uncharged, and anionic polymers showed no mucin binding. Cationic polymers also increased chymotrypsin activity from pH 6-8, while zwitterionic polymers had no effect, and uncharged and anionic polymers decreased enzyme activity. Lastly, cationic polymers decreased the tendency of chymotrypsin to structurally unfold at extremely low pH, while uncharged and anionic polymers induced unfolding more quickly. We hypothesized that when polymers are covalently attached to the surface of a protein, the degree to which those polymers interact with the protein surface is the predominant determinant of whether the polymer will stabilize or inactivate the protein. Preferential interactions between the polymer and the protein lead to removal of water from the surface of the protein, and this, we believe, inactivates the enzyme.

  8. Particle-in-a-Box Model of Exciton Absorption and Electroabsorption in Conjugated Polymers

    DEFF Research Database (Denmark)

    Pedersen, Thomas Garm

    2001-01-01

    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 ...... 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.......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...

  9. Structure and Morphology Control in Thin Films of Conjugated Polymers for an Improved Charge Transport

    Directory of Open Access Journals (Sweden)

    Haiyang Wang

    2013-11-01

    Full Text Available The morphological and structural features of the conjugated polymer films play an important role in the charge transport and the final performance of organic optoelectronics devices [such as organic thin-film transistor (OTFT and organic photovoltaic cell (OPV, etc.] in terms of crystallinity, packing of polymer chains and connection between crystal domains. This review will discuss how the conjugated polymer solidify into, for instance, thin-film structures, and how to control the molecular arrangement of such functional polymer architectures by controlling the polymer chain rigidity, polymer solution aggregation, suitable processing procedures, etc. These basic elements in intrinsic properties and processing strategy described here would be helpful to understand the correlation between morphology and charge transport properties and guide the preparation of efficient functional conjugated polymer films correspondingly.

  10. 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.

  11. Liquid scintillators with near infrared emission based on organoboron conjugated polymers.

    Science.gov (United States)

    Tanaka, Kazuo; Yanagida, Takayuki; Yamane, Honami; Hirose, Amane; Yoshii, Ryousuke; Chujo, Yoshiki

    2015-11-15

    The organic liquid scintillators based on the emissive polymers are reported. A series of conjugated polymers containing organoboron complexes which show the luminescence in the near infrared (NIR) region were synthesized. The polymers showed good solubility in common organic solvents. From the comparison of the luminescent properties of the synthesized polymers between optical and radiation excitation, similar emission bands were detected. In addition, less significant degradation was observed. These data propose that the organoboron conjugated polymers are attractive platforms to work as an organic liquid scintillator with the emission in the NIR region. Copyright © 2015 Elsevier Ltd. All rights reserved.

  12. Fluorescence Ratiometric Assay Strategy for Chemical Transmitter of Living Cells Using H2O2-Sensitive Conjugated Polymers.

    Science.gov (United States)

    Wang, Yunxia; Li, Shengliang; Feng, Liheng; Nie, Chenyao; Liu, Libing; Lv, Fengting; Wang, Shu

    2015-11-04

    A new water-soluble conjugated poly(fluorene-co-phenylene) derivative (PFP-FB) modified with boronate-protected fluorescein (peroxyfluor-1) via PEG linker has been designed and synthesized. In the presence of H2O2, the peroxyfluor-1 group can transform into green fluorescent fluorescein by deprotecting the boronate protecting groups. In this case, upon selective excitation of PFP-FB backbone at 380 nm, efficient fluorescence resonance energy transfer (FRET) from PFP-FB backbone to fluorescein occurs, and accordingly, the fluorescence color of PFP-FB changes from blue to green. Furthermore, the emission color of PFP-FB and the FRET ratio change in a concentration-dependent manner. By taking advantage of PFP-FB, ratiometric detection of choline and acetylcholine (ACh) through cascade enzymatic reactions and further dynamic monitoring of the choline consumption process of cancer cells have been successfully realized. Thus, this new polymer probe promotes the development of enzymatic biosensors and provides a simpler and more effective way for detecting the chemical transmitter of living cells.

  13. Preparation of Composite Films of a Conjugated Polymer and C60NWs and Their Photovoltaic Application

    Directory of Open Access Journals (Sweden)

    Takatsugu Wakahara

    2016-01-01

    Full Text Available Composite films of conjugated polymers, such as poly[2-methoxy-5-(3′,7′-dimethyloctyloxy-1,4-phenylenevinylene] (MDMO-PPV and poly(3-hexylthiophene (P3HT, with C60 nanowhiskers (C60NWs were prepared. The photoluminescence originating from the conjugated MDMO-PPV polymers was effectively quenched in the composite film, indicating a strong interaction between the conjugated polymer and C60NWs. The photovoltaic devices were fabricated using C60NW (conjugated polymer composite films, resulting in a power conversion efficiency of ~0.01% for P3HT with short length thin C60NWs, which is higher than that previously reported for thick C60 nanorods. The present study gives new guidance on the selection of the type of C60NWs and the appropriate polymer for new photovoltaic devices.

  14. Nanotesla magnetoresistance in π-conjugated polymer devices

    Science.gov (United States)

    Klemm, Philippe; Bange, Sebastian; Pöllmann, Agnes; Boehme, Christoph; Lupton, John M.

    2017-06-01

    We demonstrate submicrotesla sensitivity of organic magnetoresistance in thin-film diodes made of the conducting polymer poly(styrene sulfonate)-doped poly(3,4-ethylenedioxythiophene) (PEDOT:PSS). The magnetoresistance sensitivity is shown to be better than 20 parts per billion (ppb). As for other conjugated polymers, magnetoresistance can be separated into two regimes of field strength: the nonmonotonic ultrasmall magnetic field effect on magnetic field scales below 2 mT, and the monotonic intermediate magnetic field effect on scales over several tens of mT. The former gives the PEDOT:PSS magnetoresistance curve a characteristic W-shaped functionality, with inverted turning points compared to those found in conventional organic light-emitting diode (OLED) devices. We succeed in resolving the ultrasmall magnetic field effect of the PEDOT:PSS layer incorporated within an OLED structure, which is responsible for an additional magnetoresistive feature on the ppm scale. Such a device shows unprecedented complexity in magnetoresistance with a total of four extrema within a field range of ±1 mT. We propose that these unique characteristics arise from spin-spin interactions in the weakly bound carrier pairs responsible for the spin-dependent recombination probed in magnetoresistance.

  15. Control of Molecular Ordering, Alignment, and Charge Transport in Solution-Processed Conjugated Polymer Thin Films

    Directory of Open Access Journals (Sweden)

    Mincheol Chang

    2017-06-01

    Full Text Available Morphology of conjugated polymers is a critical factor that significantly affects intrinsic charge transport characteristics and in turn performance of polymer-based devices. Morphological defects including misaligned crystalline grains and grain boundaries significantly impede efficient charge hopping between transport sites, resulting in degradation of device performance. Therefore, one important challenge is to control morphology of active polymer thin-films for achieving high performance flexible electronic devices. In the past decade, significant progress has been achieved in morphology control of conjugated polymer thin-films using solution-based processing techniques. This review focuses on recent advances in processing strategies that can tune the morphologies and thus impact charge transport properties of conjugated polymer thin films. Of the available processing strategies, polymer solution treatments and film deposition techniques will be mainly highlighted. The correlation between processing conditions, active layer morphologies, and device performance will be also be discussed.

  16. Non-radiative resonance energy transfer in bi-polymer nanoparticles of fluorescent conjugated polymers.

    Science.gov (United States)

    Ozel, Ilkem Ozge; Ozel, Tuncay; Demir, Hilmi Volkan; Tuncel, Donus

    2010-01-18

    This work demonstrates the comparative studies of non-radiative resonance energy transfer in bi-polymer nanoparticles based on fluorescent conjugated polymers. For this purpose, poly[(9,9-dihexylfluorene) (PF) as a donor (D) and poly[2-methoxy-5-(2'-ethyl-hexyloxy)-1,4-phenylene vinylene] (MEH-PPV) as an acceptor (A) have been utilized, from which four different bi-polymer nanoparticle systems are designed and synthesized. Both, steady-state fluorescence spectra and time-resolved fluorescence measurements indicate varying energy transfer efficiencies from the host polymer PF to the acceptor polymer MEH-PPV depending on the D-A distances and structural properties of the nanoparticles. The first approach involves the preparation of PF and MEH-PPV nanoparticles separately and mixing them at a certain ratio. In the second approach, first PF and MEH-PPV solutions are mixed prior to nanoparticle formation and then nanoparticles are prepared from the mixture. Third and fourth approaches involve the sequential nanoparticle preparation. In the former, nanoparticles are prepared to have PF as a core and MEH-PPV as a shell. The latter is the reverse of the third in which the core is MEH-PPV and the shell is PF. The highest energy transfer efficiency recorded to be 35% is obtained from the last system, in which a PF layer is sequentially formed on MEH-PPV NPs.

  17. Phase transfer of hydrophobic QDs for water-soluble and biocompatible nature through silanization

    Energy Technology Data Exchange (ETDEWEB)

    Yang, Ping, E-mail: mse_yangp@ujn.edu.cn [School of Material Science and Engineering, University of Jinan, Jinan 250022 (China); Zhou, Guangjun [State Key Laboratory of Crystal Materials, Shandong University, Jinan 250100 (China)

    2011-12-15

    Graphical abstract: A facile and novel method has been developed for creating water-soluble and biocompatible CdSe/ZnS quantum dots with a small hydrodynamic diameter (less than 10 nm) via silanization. Highlights: Black-Right-Pointing-Pointer A facile and novel method has been developed for creating water-soluble and biocompatible CdSe/ZnS quantum dots (QDs) with a small hydrodynamic diameter (less than 10 nm). Black-Right-Pointing-Pointer The control of ligand exchange plays an important role to retain high fluorescence quantum yields. Black-Right-Pointing-Pointer The functional SiO{sub 2}-coated QDs were conjugated with immunoglobin G antibody by using biotin-streptavidin as linkers. Black-Right-Pointing-Pointer The QD phase transfer by silanization is a well-established method for generating biocompatible QDs. -- Abstract: A novel method has been developed for creating water-soluble and biocompatible CdSe/ZnS quantum dots (QDs) with a small hydrodynamic diameter (less than 10 nm). The silanization of the QDs was carried out by using partially hydrolyzed tetraethyl orthosilicate (TEOS) to replace organic ammine or tri-n-octylphosphine oxide on the surface of the QDs. The partially hydrolyzed 3-mercaptopropyltrimethoxysilane attached to the hydrolyzed TEOS layer on the QDs prevented the QDs from agglomeration when the QDs were transferred into water. The functional SiO{sub 2}-coated QDs were conjugated with immunoglobin G antibody by using biotin-streptavidin as linkers. The SiO{sub 2}-coated QDs exhibited the same absorption and photoluminescence (PL) spectra as those of initial QDs in organic solvents. The SiO{sub 2}-coated QDs preserved PL intensities, is colloidally stable over a wide pH range (pH 6-11). Because the mean diameter of amphiphilic polymer-coated QDs was almost 2 times of that of functional SiO{sub 2}-coated QDs, the QD phase transfer by silanization is a well-established method for generating biocompatible QDs.

  18. Tuning the entropic spring to dictate order and functionality in polymer conjugated peptide biomaterials

    Science.gov (United States)

    Keten, Sinan

    Hybrid peptide-polymer conjugates have the potential to combine the advantages of natural proteins and synthetic polymers, resulting in biomaterials with improved stability, controlled assembly, and tailored functionalities. However, the effect of polymer conjugation on peptide structural organization and functionality, along with the behavior of polymers at the interface with biomolecules remain to be fully understood. This talk will summarize our recent efforts towards establishing a modeling framework to design entropic forces in helix-polymer conjugates and polymer-conjugated peptide nanotubes to achieve hierarchical self-assembling systems with predictable order. The first part of the talk will discuss how self-assembly principles found in biology, combined with polymer physics concepts can be used to create artificial membranes that mimic certain features of ion channels. Thermodynamics and kinetics aspects of self-assembly and how it governs the growth and stacking sequences of peptide nanotubes will be discussed, along with its implications for nanoscale transport. The second part of the talk will review advances related to modeling polymer conjugated coiled coils at relevant length and time scales. Atomistic simulations combined with sampling techniques will be presented to discuss the energy landscapes governing coiled-coil stability, revealing cascades of events governing disassembly. This will be followed by a discussion of mechanisms through which polymers can stabilize small proteins, such as shielding of solvents, and how specific peptide sequences can reciprocate by altering polymer conformations. Correlations between mechanical and thermal stability of peptides will be discussed. Finally, coarse-grained simulations will provide insight into how the location of polymer attachment changes entropic forces and higher-level organization in helix bundle assemblies. Our findings set the stage for a materials-by-design capability towards dictating complex

  19. Photochemical Stability of π-Conjugated Polymers for Polymer Solar Cells: a Rule of Thumb

    DEFF Research Database (Denmark)

    Manceau, Matthieu

    2010-01-01

    of the moieties commonly used in the PSCs field are thus included in this study. The behavior of each material has been carefully investigated under simulated sunlight (1 sun, 1000 W m-2, AM 1.5G) and ambient atmosphere. Degradation was monitored all along ageing combining UV-visible and Infra-red spectroscopies...... of different points on photochemical stability is discussed (donor and acceptor group nature, side-chain type). This screening finally allowed for the description of general rules for π-conjugated polymer photochemical stability. Our results thus provide a better description of the structure – stability...

  20. Organic photovoltaic devices produced from conjugated polymer/methanofullerene bulk heterojunctions

    NARCIS (Netherlands)

    Brabec, C.J.; Shaheen, S.E.; Fromherz, T.; Padinger, F.; Hummelen, J.C.; Dhanabalan, A.; Janssen, R.A.J.; Sariciftci, N.S.

    2001-01-01

    Organic photovoltaic devices have been fabricated utilizing the photoinduced electron transfer with long-living charge separation in conjugated polymer/methanofullerene thin films. The performance of such "bulk heterojunction" photovoltaic devices is critically dependent on the charge transport

  1. Switching between H- and J-type electronic coupling in single conjugated polymer aggregates

    National Research Council Canada - National Science Library

    Theresa Eder; Thomas Stangl; Max Gmelch; Klaas Remmerssen; Dirk Laux; Sigurd Höger; John M Lupton; Jan Vogelsang

    2017-01-01

    .... Here we report that the predominant coupling in isolated aggregates of conjugated polymers can be switched reversibly between H-type and J-type coupling by partially swelling and drying the aggregates...

  2. Array-based sensing of normal, cancerous, and metastatic cells using conjugated fluorescent polymers.

    Science.gov (United States)

    Bajaj, Avinash; Miranda, Oscar R; Phillips, Ronnie; Kim, Ik-Bum; Jerry, D Joseph; Bunz, Uwe H F; Rotello, Vincent M

    2010-01-27

    A family of conjugated fluorescent polymers was used to create an array for cell sensing. Fluorescent conjugated polymers with pendant charged residues provided multivalent interactions with cell membranes, allowing the detection of subtle differences between different cell types on the basis of cell surface features. Highly reproducible characteristic patterns were obtained from different cell types as well as from isogenic cell lines, enabling the identification of the cell type as well differentiating between normal, cancerous, and metastatic isogenic cell types with high accuracy.

  3. Spiro-linked hyperbranched architecture in electrophosphorescent conjugated polymers for tailoring triplet energy back transfer.

    Science.gov (United States)

    Shao, Shiyang; Ma, Zhihua; Ding, Junqiao; Wang, Lixiang; Jing, Xiabin; Wang, Fosong

    2012-04-17

    A spiro-linked hyperbranched architecture has been incorporated into electrophosphorescent conjugated polymers for the first time, aiming at simultaneously tailoring the intra- and intermolecular triplet energy back transfer from the phosphorescent guest to the conjugated polymer host. Based on a prototype with this unique structure, slower decay of triplet excitons, and 5-8 fold enhancement of device efficiencies are obtained compared with the conventional blending counterpart. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  4. D-A conjugated polymers containing substituted thiophene, 1,3,4 ...

    Indian Academy of Sciences (India)

    s12039-016-1145-6. D-A conjugated polymers containing substituted thiophene,. 1,3,4-oxadiazole and non-conjugation linkers: Synthesis and study of optical and electrochemical properties. PRASHANTH KUMAR K Ra, UDAYAKUMAR Da,∗ ...

  5. Simplified Models for Accelerated Structural Prediction of Conjugated Semiconducting Polymers

    Energy Technology Data Exchange (ETDEWEB)

    Henry, Michael M. [Micron; Jones, Matthew L. [Micron; Oosterhout, Stefan D. [National Renewable Energy Laboratory, Golden, Colorado 80401, United States; Braunecker, Wade A. [National Renewable Energy Laboratory, Golden, Colorado 80401, United States; Kemper, Travis W. [National Renewable Energy Laboratory, Golden, Colorado 80401, United States; Larsen, Ross E. [National Renewable Energy Laboratory, Golden, Colorado 80401, United States; Kopidakis, Nikos [National Renewable Energy Laboratory, Golden, Colorado 80401, United States; Department; Toney, Michael F. [SLAC National Accelerator Laboratory, Menlo Park, California 94025, United States; Olson, Dana C. [National Renewable Energy Laboratory, Golden, Colorado 80401, United States; Jankowski, Eric [Micron; National Renewable Energy Laboratory, Golden, Colorado 80401, United States

    2017-11-20

    We perform molecular dynamics simulations of poly(benzodithiophene-thienopyrrolodione) (BDT-TPD) oligomers in order to evaluate the accuracy with which unoptimized molecular models can predict experimentally characterized morphologies. The predicted morphologies are characterized using simulated grazing-incidence X-ray scattering (GIXS) and compared to the experimental scattering patterns. We find that approximating the aromatic rings in BDT-TPD with rigid bodies, rather than combinations of bond, angle, and dihedral constraints, results in 14% lower computational cost and provides nearly equivalent structural predictions compared to the flexible model case. The predicted glass transition temperature of BDT-TPD (410 +/- 32 K) is found to be in agreement with experiments. Predicted morphologies demonstrate short-range structural order due to stacking of the chain backbones (p-p stacking around 3.9 A), and long-range spatial correlations due to the self-organization of backbone stacks into 'ribbons' (lamellar ordering around 20.9 A), representing the best-to-date computational predictions of structure of complex conjugated oligomers. We find that expensive simulated annealing schedules are not needed to predict experimental structures here, with instantaneous quenches providing nearly equivalent predictions at a fraction of the computational cost of annealing. We therefore suggest utilizing rigid bodies and fast cooling schedules for high-throughput screening studies of semiflexible polymers and oligomers to utilize their significant computational benefits where appropriate.

  6. Characterization of conjugated polymer actuation under cerebral physiological conditions.

    Science.gov (United States)

    Daneshvar, Eugene Dariush; Smela, Elisabeth

    2014-07-01

    Conjugated polymer actuators have potential use in implantable neural interface devices for modulating the position of electrode sites within brain tissue or guiding insertion of neural probes along curved trajectories. The actuation of polypyrrole (PPy) doped with dodecylbenzenesulfonate (DBS) is characterized to ascertain whether it can be employed in the cerebral environment. Microfabricated bilayer beams are electrochemically cycled at either 22 or 37 °C in aqueous NaDBS or in artificial cerebrospinal fluid (aCSF). Nearly all the ions in aCSF are exchanged into the PPy-the cations Na(+) , K(+) , Mg(2+) , Ca(2+) , as well as the anion PO4 (3-) ; Cl(-) is not present. Nevertheless, deflections in aCSF are comparable to those in NaDBS and they are monotonic with oxidation level: strain increases upon reduction, with no reversal of motion despite the mixture of ionic charges and valences being exchanged. Actuation depends on temperature. Upon warming, the cyclic voltammograms show additional peaks and an increase of 70% in the consumed charge. Bending is, however, much less affected: strain increases somewhat (6%-13%) but remains monotonic, and deflections shift (up to 20%). These results show how the actuation environment must be taken into account, and demonstrate proof of concept for actuated implantable neural interfaces. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. Controlled Radical Polymerization as an Enabling Approach for the Next Generation of Protein-Polymer Conjugates.

    Science.gov (United States)

    Pelegri-O'Day, Emma M; Maynard, Heather D

    2016-09-20

    Protein-polymer conjugates are unique constructs that combine the chemical properties of a synthetic polymer chain with the biological properties of a biomacromolecule. This often leads to improved stabilities, solubilities, and in vivo half-lives of the resulting conjugates, and expands the range of applications for the proteins. However, early chemical methods for protein-polymer conjugation often required multiple polymer modifications, which were tedious and low yielding. To solve these issues, work in our laboratory has focused on the development of controlled radical polymerization (CRP) techniques to improve synthesis of protein-polymer conjugates. Initial efforts focused on the one-step syntheses of protein-reactive polymers through the use of functionalized initiators and chain transfer agents. A variety of functional groups such as maleimide and pyridyl disulfide could be installed with high end-group retention, which could then react with protein functional groups through mild and biocompatible chemistries. While this grafting to method represented a significant advance in conjugation technique, purification and steric hindrance between large biomacromolecules and polymer chains often led to low conjugation yields. Therefore, a grafting from approach was developed, wherein a polymer chain is grown from an initiating site on a functionalized protein. These conjugates have demonstrated improved homogeneity, characterization, and easier purification, while maintaining protein activity. Much of this early work utilizing CRP techniques focused on polymers made up of biocompatible but nonfunctional monomer units, often containing oligoethylene glycol meth(acrylate) or N-isopropylacrylamide. These branched polymers have significant advantages compared to the historically used linear poly(ethylene glycols) including decreased viscosities and thermally responsive behavior, respectively. Recently, we were motivated to use CRP techniques to develop polymers with

  8. Photocatalysts Based on Cobalt-chelating Conjugated Polymers for Hydrogen Evolution from Water

    Energy Technology Data Exchange (ETDEWEB)

    Li, Lianwei; Hadt, Ryan G.; Yao, Shiyu; Lo, Waiyip; Cai, Zhengxu; Wu, Qingliu; Pandit, Bill; Chen, Lin X.; Yu, Luping

    2016-08-09

    Developing photocatalytic systems for water splitting to generate oxygen and hydrogen is one of the biggest chemical challenges in solar energy utilization. In this work, we report the first example of heterogeneous photocatalysts for hydrogen evolution based on in-chain cobalt-chelating conjugated polymers. Four conjugated polymers chelated with earth abundant cobalt ions were synthesized and found to evolve hydrogen photocatalytically from water. These polymers are designed to combine functions of the conjugated backbone as light-harvesting antenna and electron transfer conduit with the in-chain bipyridyl chelated transition metal centers as catalytic active sites. In addition, these polymers are soluble in organic solvents, enabling effective interactions with the substrates as well as detailed characterization. We also found a polymer-dependent optimal cobalt chelating concentration at which the highest photocatalytic hydrogen production (PHP) activity can be achieved.

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

    Science.gov (United States)

    Xu, Lirong; Yang, Liu; Lei, Shengbin

    2012-07-01

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

  10. Studies of photoinduced charge transfer in conjugated polymer-fullerene composites by light-induced ESR

    NARCIS (Netherlands)

    Dyakonov, V.; Zoriniants, G.; Scharber, M.; Brabec, C.J.; Janssen, R.A.J.; Hummelen, J.C.; Sariciftci, N.S.

    1998-01-01

    In this work we present comparative studies of the photoinduced electron transfer (PIT) in a number of conjugated polymer/fullerene composites and in pure components by using light-induced electron spin resonance. PIT from the polymer onto fullerene in the composites results in the appearance of two

  11. Star Polymer-Drug Conjugates with pH-Controlled Drug Release and Carrier Degradation

    Directory of Open Access Journals (Sweden)

    H. Kostková

    2017-01-01

    Full Text Available In this study, we describe the design, synthesis, and physicochemical and preliminary biological characteristics of new biodegradable, high-molecular-weight (HMW drug delivery systems with star-like architectures bearing the cytotoxic drug doxorubicin (DOX attached by a hydrazone bond-containing spacer. The star polymers were synthesized by grafting semitelechelic N-(2-hydroxypropyl methacrylamide (HPMA copolymers on a 2,2-bis(hydroxymethylpropionic acid- (bis-MPA- based polyester dendritic core. The molecular weight of the star polymers ranged from 280 to 450 000 g/mol and could be adjusted by proper selection of the bis-MPA dendrimer generation and by considering the polymer to dendrimer molar ratio. The biodegradation of the polymer conjugates is based on the spontaneous slow hydrolysis of the dendritic core in neutral physiological conditions. Hydrazone spacers in the conjugates were fairly stable at neutral pH (7.4 mimicking blood stream conditions, and DOX was released from the conjugates under mild acidic conditions simulating the tumor cell microenvironment in endosomes and lysosomes (pH 5. Finally, we have shown the significant in vitro cytotoxicity of the star polymer-DOX conjugate on selected cancer cell lines with IC50 values almost comparable with that of the free drug and higher than that observed for a linear polymer-DOX conjugate with much lower molecular weight.

  12. Label-free, real-time multiplexed DNA detection using fluorescent conjugated polymers.

    Science.gov (United States)

    Zheng, Weiming; He, Lin

    2009-03-18

    A label-free, multiplexed DNA assay using fluorescent conjugated polymers as a detection probe to illustrate hybridization on metallic striped nanorods is demonstrated. Different DNA capture probes were encoded by the different reflectivities of Au and Ag stripe patterns. Successful DNA hybridization induced an optically detectable conformational change in conjugated polythiophene derivatives from forming single-stranded DNA-polymer complexes to forming double-stranded DNA-polymer ones. The results show attomole detection sensitivity and single-mutation specificity comparable to those of single-element assays but with much improved throughput.

  13. 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.

  14. Narrow Gap, High Mobility, and Stable Pi Conjugated Polymers

    Science.gov (United States)

    2012-09-20

    Efficiency Inverted Polymer Solar Cells with Double Interlayer” Conference... Efficient Inverted Polymer Solar Cells using Silole-containing low-bandgap polymer ” with C. Small, F. So. 18. Materials Research...to be used as the active polymer in PCBM based solar cells . 6 Simplifying our chemistry, we have developed Stille coupling polymerization

  15. Synthesis of graphene-conjugated polymer nanocomposites for electronic device applications.

    Science.gov (United States)

    Qi, Xiaoying; Tan, Chaoliang; Wei, Jun; Zhang, Hua

    2013-02-21

    Graphene-based polymer nanocomposites have attracted increasing interest because of their superior physicochemical properties over polymers. Semiconductor conjugated polymers (CPs) with excellent dispersibility and stability, and efficient electronic and optical properties have been recently integrated with graphene to form a new class of functional nanomaterials. In this minireview, we will summarize the recent advances in the development of graphene-CP nanocomposites for electronic device applications.

  16. 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: e0118824

    National Research Council Canada - National Science Library

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

    2015-01-01

    .... 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...

  17. 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

    National Research Council Canada - National Science Library

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

    2015-01-01

    .... 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...

  18. Homogeneous fluorescent specific PCR for the authentication of medicinal snakes using cationic conjugated polymers.

    Science.gov (United States)

    Jiang, Chao; Yuan, Yuan; Liu, Libing; Hou, Jingyi; Jin, Yan; Huang, Luqi

    2015-11-05

    A label-free, homogenous and sensitive one-step method for the molecular authentication of medicinal snakes has been developed by combining a rapid PCR technique with water-soluble cationic conjugated polyelectrolytes (CCPs). Three medicinal snake materials (Deinagkistrodon acutus, Zaocys dhumnades and Bungarus multicinctus; a total of 35 specimens) and 48 snake specimens with similar morphologies and textures were clearly distinguished by the naked eye by utilizing a CCP-based assay in a high-throughput manner. The identification of medicinal snakes in patented Chinese drugs was successfully performed using this detection system. In contrast to previous fluorescence-labeled oligonucleotide detection and direct DNA stain hybridization assays, this method does not require designing dye-labeled primers, and unfavorable dimer fluorescence is avoided in this homogenous method.

  19. Biodegradable star HPMA polymer-drug conjugates: Biodegradability, distribution and anti-tumor efficacy.

    Science.gov (United States)

    Etrych, Tomáš; Kovář, Lubomír; Strohalm, Jiří; Chytil, Petr; Ríhová, Blanka; Ulbrich, Karel

    2011-09-25

    Herein, new biodegradable star polymer-doxorubicin conjugates designed for passive tumor targeting were investigated, and their synthesis, physico-chemical characterization, drug release, biodegradation, biodistribution and in vivo anti-tumor efficacy are described. In the conjugates, the core formed by poly(amidoamine) (PAMAM) dendrimers was grafted with semitelechelic N-(2-hydroxypropyl)methacrylamide (HPMA) copolymers bearing doxorubicin (Dox) attached by hydrazone bonds, which enabled intracellular pH-controlled drug release. The described synthesis facilitated the preparation of biodegradable polymer conjugates in a broad range of molecular weights (200-1000g/mol) while still maintaining low polydispersity (~1.7). The polymer grafts were attached to the dendrimers through either stable amide bonds or enzymatically or reductively degradable spacers, which enabled intracellular degradation of the high-molecular-weight polymer carrier to excretable products. Biodegradability tests in suspensions of EL4 T-cell lymphoma cells showed that the rate of degradation was much faster for reductively degradable conjugates (close to completion within 24h of incubation) than for conjugates linked via an enzymatically degradable oligopeptide GFLG sequence (slow degradation taking several days). This finding was likely due to the differences in steric hindrance in terms of the accessibility of the small molecule glutathione and the bulky enzyme cathepsin B to the polymer substrate. Regarding drug release, the conjugates were fairly stable in buffer at pH 7.4 (model of blood stream) but released doxorubicin under mild acidic conditions that model the tumor cell microenvironment. The star polymer-Dox conjugates exhibited significantly prolonged blood circulation and enhanced tumor accumulation in tumor-bearing mice, indicating the important role of the EPR effect in its anti-cancer activity. The star polymer conjugates showed prominently higher in vivo anti-tumor activities than

  20. 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.

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

    Science.gov (United States)

    Lidický, O; Šírová, M; Etrych, T

    2016-10-20

    In this paper, we describe the synthesis, physicochemical characterization, drug release kinetics and preliminary biological evaluation of several N-(2-hydroxypropyl)methacrylamide (HPMA)-based polymer-retinoid conjugates designed for solid tumor immunotherapy. The conjugates are supposed to inhibit the immunosuppressive activity of myeloid-derived suppressor cells (MDSC) accumulated in the solid tumor microenvironment. All-trans retinoic acid (ATRA) was derivatized to hydrazide (AtrHy) and then attached to the polymer backbone via a spacer that is stable at the normal pH of blood (7.4) and hydrolytically degradable in mildly acidic environments (e.g. in endosomes or lysosomes, pH~5.0-6.5). Polymer-AtrHy conjugates were designed to achieve prolonged blood circulation and release of the immunomodulator intracellularly or extracellularly in solid tumor tissue. Three types of polymer precursors, differing in the structure of the keto acid-containing side chains, were synthesized. A linkage susceptible to hydrolytic cleavage was formed by the conjugation reaction of the carbonyl group-terminated side chains of the polymer precursors with the hydrazide group of a drug derivative. In vitro incubation of the conjugates in buffers resulted in much faster release of the drugs or their derivatives from the polymer at pH 5.0 than at pH 7.4, with the rate depending on the detailed structure of the spacer. Both the AtrHy derivative and its polymer conjugates showed the ability to induce the differentiation of retinoid-responsive HL-60 cells, thus demonstrating the required biological activity.

  2. Impact of the Crystallite Orientation Distribution on Exciton Transport in Donor-Acceptor Conjugated Polymers.

    Science.gov (United States)

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

    2015-12-30

    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.

  3. 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.

  4. Conjugated polymer/nanocrystal nanocomposites for renewable energy applications in photovoltaics and photocatalysis.

    Science.gov (United States)

    Su, Yu-Wei; Lin, Wei-Hao; Hsu, Yung-Jung; Wei, Kung-Hwa

    2014-11-01

    Conjugated polymer/nanocrystal composites have attracted much attention for use in renewable energy applications because of their versatile and synergistic optical and electronic properties. Upon absorbing photons, charge separation occurs in the nanocrystals, generating electrons and holes for photocurrent flow or reduction/oxidation (redox) reactions under proper conditions. Incorporating these nanocrystals into conjugated polymers can complement the visible light absorption range of the polymers for photovoltaics applications or allow the polymers to sensitize or immobilize the nanocrystals for photocatalysis. Here, the current developments of conjugated polymer/nanocrystal nanocomposites for bulk heterojunction-type photovoltaics incorporating Cd- and Pb-based nanocrystals or quantum dots are reviewed. The effects of manipulating the organic ligands and the concentration of the nanocrystal precursor, critical factors that affect the shape and aggregation of the nanocrystals, are also discussed. In the conclusion, the mechanisms through which conjugated polymers can sensitize semiconductor nanocrystals (TiO2 , ZnO) to ensure efficient charge separation, as well as how they can support immobilized nanocrystals for use in photocatalysis, are addressed. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  5. Capture and conversion of CO2 at ambient conditions by a conjugated microporous polymer

    Science.gov (United States)

    Xie, Yong; Wang, Ting-Ting; Liu, Xiao-Huan; Zou, Kun; Deng, Wei-Qiao

    2013-01-01

    Conjugated microporous polymers are a new class of porous materials with an extended π-conjugation in an amorphous organic framework. Owing to the wide-ranging flexibility in the choice and design of components and the available control of pore parameters, these polymers can be tailored for use in various applications, such as gas storage, electronics and catalysis. Here we report a class of cobalt/aluminium-coordinated conjugated microporous polymers that exhibit outstanding CO2 capture and conversion performance at atmospheric pressure and room temperature. These polymers can store CO2 with adsorption capacities comparable to metal-organic frameworks. The cobalt-coordinated conjugated microporous polymers can also simultaneously function as heterogeneous catalysts for the reaction of CO2 and propylene oxide at atmospheric pressure and room temperature, wherein the polymers demonstrate better efficiency than a homogeneous salen-cobalt catalyst. By combining the functions of gas storage and catalysts, this strategy provides a direction for cost-effective CO2 reduction processes. PMID:23727768

  6. DA conjugated polymers containing substituted thiophene, 1, 3, 4 ...

    Indian Academy of Sciences (India)

    Fluorescence emission studies revealed that the polymer thin films emit intense blue light with emission maxima in the wavelength rage 430–480 nm. All three polymers undergo both oxidation and reduction processes under electrochemical conditions. Further, these polymers (P1–P3) exhibit low-lying HOMO and LUMO ...

  7. 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.

  8. 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...... character of the polaronic charge carriers, which exhibit lower relaxation energies than the corresponding radical cations on isolated one-dimensional chains. The possibility of achieving high mobilities via two-dimensional transport in self-organized conjugated lamellae is important for applications...

  9. 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.

  10. Synthesis and evaluation of PEG-O-chitosan nanoparticles for delivery of poor water soluble drugs: Ibuprofen

    Energy Technology Data Exchange (ETDEWEB)

    Hassani Najafabadi, Alireza [Department of Chemistry, Amirkabir University of Technology, P.O. Box 1587-4413, Tehran (Iran, Islamic Republic of); Abdouss, Majid, E-mail: phdabdouss44@aut.ac.ir [Department of Chemistry, Amirkabir University of Technology, P.O. Box 1587-4413, Tehran (Iran, Islamic Republic of); Faghihi, Shahab [Tissue Engineering and Biomaterials Division, National Institute of Genetic Engineering and Biotechnology, Tehran 14965/161 (Iran, Islamic Republic of)

    2014-08-01

    Current methods for preparation of PEGylated chitosan have limitations such as harsh de protecting step and several purification cycles. In the present study, a facile new method for conjugating methoxy polyethylene glycol (mPEG) to chitosan under mild condition is introduced to improve water solubility of chitosan and control the release of poor water soluble drugs. The method consists of chitosan modification by grafting the C6 position of chitosan to mPEG which is confirmed by Fourier transformed-infrared (FT-IR) and proton nuclear magnetic resonance ({sup 1}HNMR) analyses. The amine groups at the C2 position of chitosan are protected using sodium dodecylsulfate (SDS) which is removed by dialyzing the precipitation against Tris solution. The chemical structure of the prepared polymer is characterized by FTIR and {sup 1}HNMR. The synthesized polymer is then employed to prepare nanoparticles which are characterized by transmission electron microscopy (TEM), atomic force microscopy (AFM), scanning electron microscopy (SEM), and dynamic light scattering (DLS) for their size and morphology. The nanoparticles are used for encapsulation of ibuprofen followed by in vitro release investigation in gastrointestinal and simulated biological fluids. The chitosan nanoparticles are used as control. The PEGylated nanoparticles show a particle size of 80 nm with spherical morphology. The results clearly show that drug release from PEGylated chitosan nanoparticles is remarkably slower than chitosan. In addition, drug encapsulation and encapsulation efficiency in PEGylated nanoparticles are dependent on the amount of drug added to the formulation being significantly higher than chitosan nanoparticles. This study provides an efficient, novel, and facile method for preparing a nano carrier system for delivery of water insoluble drugs. - Highlights: • A facile novel method for conjugating methoxy polyethylene glycol (mPEG) to chitosan is introduced. • Fabricated PEG

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

    Directory of Open Access Journals (Sweden)

    Stoichko D. Dimitrov

    2016-01-01

    Full Text Available 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.

  12. 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.

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

    CERN Document Server

    Matterson, B J

    2002-01-01

    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. 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 fou...

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

    Science.gov (United States)

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

    1998-08-01

    Various interesting photophysical phenomena in composites of fullerenes and non degenerate ground state conjugated polymers with highly extended π-electrons in their main chain can be explained by the ultrafast electron transfer from the conjugated polymer (donor) to the fullerene (acceptor) upon illumination. This photoeffect was utilized for the production of small area (mm2) photovoltaic devices which show energy conversion efficiencies ηe>1% and carrier collection efficiencies ηc>20%. In this work we present efficiency and stability studies on large area (6 cm by 6 cm) flexible solar cells based on a soluble alkoxy PPV (3,7-dimethyloctyloxy methyloxy poly(phenylenevinylene)) and a highly soluble fullerene derivative, 1-(3-methoxycarbonyl)propyl-1 phenyl [5,6]C61 (PCBM). The enhanced solubility of PCBM compared to C60 allows a high fullerene-conjugated polymer ratio and strongly supports the formation of donor-acceptor bulk heterojunctions.

  15. 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.

  16. Beyond superquenching: Hyper-efficient energy transfer from conjugated polymers to gold nanoparticles

    Science.gov (United States)

    Fan, Chunhai; Wang, Shu; Hong, Janice W.; Bazan, Guillermo C.; Plaxco, Kevin W.; Heeger, Alan J.

    2003-01-01

    Gold nanoparticles quench the fluorescence of cationic polyfluorene with Stern–Volmer constants (KSV) approaching 1011 M—1, several orders of magnitude larger than any previously reported conjugated polymer–quencher pair and 9–10 orders of magnitude larger than small molecule dye–quencher pairs. The dependence of KSV on ionic strength, charge and conjugation length of the polymer, and the dimensions (and thus optical properties) of the nanoparticles suggests that three factors account for this extraordinary efficiency: (i) amplification of the quenching via rapid internal energy or electron transfer, (ii) electrostatic interactions between the cationic polymer and anionic nanoparticles, and (iii) the ability of gold nanoparticles to quench via efficient energy transfer. As a result of this extraordinarily high KSV, quenching can be observed even at subpicomolar concentrations of nanoparticles, suggesting that the combination of conjugated polymers with these nanomaterials can potentially lead to improved sensitivity in optical biosensors. PMID:12750470

  17. Molecular Recognition and Immobilization of Ligand-Conjugated Redox-Responsive Polymer Nanocontainers.

    Science.gov (United States)

    de Vries, Wilke C; Tesch, Matthias; Studer, Armido; Ravoo, Bart Jan

    2017-12-06

    We present the preparation of ligand-conjugated redox-responsive polymer nanocontainers by the supramolecular decoration of cyclodextrin vesicles with a thin redox-cleavable polymer shell that displays molecular recognition units on its surface. Two widely different recognition motifs (mannose-Concanavalin A and biotin-streptavidin) are compared and the impact of ligand density on the nanocontainer surface as well as an additional functionalization with nonadhesive poly(ethylene glycol) is studied. Aggregation assays, dynamic light scattering, and a fluorometric quantification reveal that the molecular recognition of ligand-conjugated polymer nanocontainers by receptor proteins is strongly affected by the multivalency of interactions and the association strength of the recognition motif. Finally, microcontact printing is used to prepare streptavidin-patterned surfaces, and the specific immobilization of biotin-conjugated nanocontainers is demonstrated. As a prototype of a nanosensor, these tethered nanocontainers can sense a reductive environment and react by releasing a payload.

  18. Design, synthesis, and structure-property relationships of isoindigo-based conjugated polymers.

    Science.gov (United States)

    Lei, Ting; Wang, Jie-Yu; Pei, Jian

    2014-04-15

    Conjugated polymers have developed rapidly due to their promising applications in low-cost, lightweight, and flexible electronics. The development of the third-generation donor-acceptor (D-A) polymers greatly improved the device performance in organic solar cells (OSCs) and field-effect transistors (FETs). However, for further improvement of device performance, scientists need to develop new building blocks, in particular electron-deficient aromatics, and gain an in-depth understanding of the structure-property relationships. Recently, isoindigo has been used as a new acceptor of D-A conjugated polymers. An isomer of indigo, isoindigo is a less well-known dye and can be isolated as a by-product from certain biological processes. It has two lactam rings and exhibits strong electron-withdrawing character. This electron deficiency gives isoindigo-based polymers intriguing properties, such as broad absorption and high open circuit voltage in OSCs, as well as high mobility and good ambient stability in FETs. In this Account, we review our recent progress on the design, synthesis, and structure-property relationship study of isoindigo-based polymers for FETs. Starting with some discussion on carrier transport in polymer films, we provide some basic strategies towards high-performance polymer FETs. We discuss the stability issue of devices, the impediment of the alkyl side chains, and the choice of the donor part of conjugated polymers. We demonstrate that introducing the isoindigo core effectively lowers the HOMO levels of polymers and provides FETs with long-time stability. In addition, we have found that when we use inappropriate alkyl side chains or non-centrosymmetric donors, the device performance of isoindigo polymers suffers. To further improve device performance and ambient stability, we propose several design strategies, such as using farther branched alkyl chains, modulating polymer energy levels, and extending π-conjugated backbones. We have found that using

  19. Multi-modal switching in responsive DNA block co-polymer conjugates.

    Science.gov (United States)

    Yaşayan, Gökçen; Magnusson, Johannes P; Sicilia, Giovanna; Spain, Sebastian G; Allen, Stephanie; Davies, Martyn C; Alexander, Cameron

    2013-10-14

    New classes of information-rich DNA block co-polymer conjugates were synthesised, encoded with thermoresponsive and biocompatible poly(tri(ethylene glycol)ethyl ether methacrylate) (pTriEGMA) chains and oligomeric nucleic acids connected by either bioreducible or non-reducible links. The pTriEGMA chains were grown from initiator-functionalised hybridised DNA, designed to assemble with toehold overhangs. Functional information in the conjugates was explored via dynamic light scattering (DLS) and atomic force microscopy (AFM), in order to evaluate (i) reversible self-assembly into supramolecular structures across the pTriEGMA phase transition temperature; (ii) conformational change via addition of competing DNA sequences across the toeholds, and (iii) reductive cleavage of polymer-DNA links. The results showed that discrete nanoscale conjugates could reversibly associate through pTriEGMA phase behaviour and that size and association behaviour in one class of conjugate could be switched by addition of a competing DNA sequence and by reduction to break the polymer-DNA links. Preliminary experiments with the DNA-conjugates as delivery systems for doxorubicin to a cancer cell line indicated good tolerability of the conjugates alone and cytotoxic efficacy when loaded with the drug.

  20. Array Based Sensing of Normal, Cancerous and Metastatic Cells using Conjugated Fluorescent Polymers

    Science.gov (United States)

    Bajaj, Avinash; Miranda, Oscar R.; Phillips, Ronnie; Kim, Ik-Bum; Jerry, D. Joseph; Bunz, Uwe H. F.; Rotello, Vincent M.

    2010-01-01

    A family of conjugated fluorescent polymers was used to create an array for cell sensing. Fluorescent conjugated polymers with pendant charged residues provided multivalent interactions with cell membranes, allowing the detection of subtle differences between different cell types on the basis of cell surface characteristics. Highly reproducible characteristic patterns were obtained from different cell types as well as from isogenic cell lines, enabling the identification of cell type as well differentiating between normal, cancerous and metastatic isogenic cell types with high accuracy. PMID:20039629

  1. Highly fluorescent core-shell hybrid nanoparticles templated by a unimolecular star conjugated polymer for a biological tool.

    Science.gov (United States)

    Qiu, Feng; Zhu, Qi; Tong, Gangsheng; Zhu, Lijuan; Wang, Dali; Yan, Deyue; Zhu, Xinyuan

    2012-12-21

    Highly fluorescent core-shell hybrid nanoparticles were readily fabricated from the soft template of a unimolecular star conjugated polymer (HCP-star-PDMAEMA). Since the hyperbranched conjugated polymer (HCP) core was isolated by a silicon dioxide (SiO(2)) shell, HCP@SiO(2) with excellent optical properties was retained in the aqueous solution for potential application in biological imaging.

  2. 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.

  3. Transformation of regioregular organotitanium polymers into group 16 heterole-containing π-conjugated materials.

    Science.gov (United States)

    Nishiyama, Hiroki; Kino, Tomoko; Tomita, Ikuyoshi

    2012-04-13

    Regioregular organometallic polymers with titanacyclopentadiene units, obtained from terminal diynes and a low-valent titanium complex, were subjected to reactions with disulfur dichloride and selenium (I) chloride to give π-conjugated polymers with thiophene and selenophene units in the main chain in 63% and 86% yields. Their number-average molecular weights were estimated as 4300 and 5700, respectively. Both polymers were found to be fully π-conjugated and their HOMO energy levels were remarkably high (-5.3 eV and -5.0 eV for thiophene- and selenophene-containing polymers, respectively) as supported by their UV-vis absorption spectra and CV analyses. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  4. 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.

  5. Water-soluble plasmonic nanosensors with synthetic receptors for label-free detection of folic acid.

    Science.gov (United States)

    Ahmad, Randa; Félidj, Nordin; Boubekeur-Lecaque, Leïla; Lau-Truong, Stéphanie; Gam-Derouich, Sarra; Decorse, Philippe; Lamouri, Aazdine; Mangeney, Claire

    2015-06-14

    We describe an original approach to graft molecularly imprinted polymers around gold nanorods by combining the diazonium salt chemistry and the iniferter method. This chemical strategy enables fine control of the imprinting process at the nanometer scale and provides water-soluble plasmonic nanosensors.

  6. METAL-CONTAINING CONJUGATED POLYMERS AS FLUORESCENT CHEMOSENSORS IN THE DETECTION OF TOXICANTS

    OpenAIRE

    Fegley, Megan E. A.; Pinnock, Sherryllene S.; Malele, Catherine N.; Jones, Wayne E.

    2012-01-01

    Fluorescent conjugated polymers have received a great deal of recent interest due to their ability to act as chemosensors to detect various chemical species in both environmental and biological systems with sensitivity and selectivity. Examples from the literature include polymer chemosensors that operate on either fluorescence “turn-on” or “turn-off” as mechanisms of sensor response. These responses can be related to either photoinduced electron transfer or electronic energy transfer mechani...

  7. Photoluminescence of conjugated polymer blends at the nanoscale

    NARCIS (Netherlands)

    Jarzab, Dorota; Lu, Mingtao; Nicolai, Herman T.; Blom, Paul W. M.; Loi, Maria A.

    2011-01-01

    Here we report on a combined photoluminescence and morphological study of a polymer-polymer blend composed of a copolymer of derivatives of polyspirobifluorene and polyfluorene (PBFF) and a derivative of polyphenylene vinylene (MDMO-PPV). Evidence of partial Forster energy transfer from PBFF to

  8. Photoluminescence of conjugated polymer blends at the nanoscale

    NARCIS (Netherlands)

    Jarzab, D.; Lu, M.; Nicolai, H.T.; Blom, P.W.M.; Loi, M.A.

    2011-01-01

    Here we report on a combined photoluminescence and morphological study of a polymer-polymer blend composed of a copolymer of derivatives of polyspirobifluorene and polyfluorene (PBFF) and a derivative of polyphenylene vinylene (MDMO-PPV). Evidence of partial Förster energy transfer from PBFF to

  9. Low-bandgap conjugated polymers enabling solution-processable tandem solar cells

    Science.gov (United States)

    Li, Gang; Chang, Wei-Hsuan; Yang, Yang

    2017-08-01

    The technology of polymer-based organic photovoltaic (OPV) cells has made great progress in the past decade, with the power conversion efficiency increasing from just a few per cent to around 12%, and the stability increasing from hours to years. One of the important milestones in this progress has been the invention of infrared-absorbing low-bandgap polymers, which allows the OPV cells to form effective tandem structures for harvesting near-infrared energy from the solar spectrum. In this Review, we focus on the progress in low-bandgap conjugated polymers and several tandem OPV cells enabled by these low-bandgap polymers. Specifically, we cover polymer-based tandem solar cells; hybrid tandem solar cells combining polymers with hydrogenated amorphous silicon; and unconventional solar cells. For each of these technologies, we address the challenges and offer our perspectives for future development.

  10. Method of cross-linking polyvinyl alcohol and other water soluble resins

    Science.gov (United States)

    Phillipp, W. H.; May, C. E.; Hsu, L. C.; Sheibley, D. W. (Inventor)

    1980-01-01

    A self supporting sheet structure comprising a water soluble, noncrosslinked polymer such as polyvinyl alcohol which is capable of being crosslinked by reaction with hydrogen atom radicals and hydroxyl molecule radicals is contacted with an aqueous solution having a pH of less than 8 and containing a dissolved salt in an amount sufficient to prevent substantial dissolution of the noncrosslinked polymer in the aqueous solution. The aqueous solution is then irradiated with ionizing radiation to form hydrogen atom radicals and hydroxyl molecule radicals and the irradiation is continued for a time sufficient to effect crosslinking of the water soluble polymer to produce a water insoluble polymer sheet structure. The method has particular application in the production of battery separators and electrode envelopes for alkaline batteries.

  11. Migration-assisted energy transfer at conjugated polymer/metal interfaces

    NARCIS (Netherlands)

    Markov, DE; Blom, PWM

    2005-01-01

    The dynamics of exciton quenching in a conjugated polymer due to the presence of metal films is analyzed using time-resolved photoluminescence. The quenching is governed by direct radiationless energy transfer to the metal and is further enhanced by diffusion of excitons into the depletion area of

  12. 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

  13. Click-chemistry approaches to π-conjugated polymers for organic electronics applications.

    Science.gov (United States)

    Marrocchi, Assunta; Facchetti, Antonio; Lanari, Daniela; Santoro, Stefano; Vaccaro, Luigi

    2016-10-01

    Given the wide utility of click-chemistry reactions for the preparation of simple moieties within large architecturally complex materials, this minireview article aims at surveying papers exploring their scope in the area of π-conjugated polymers for application in organic electronics to enable advanced functional properties.

  14. 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

  15. Measuring Exciton Diffusion in Conjugated Polymer Films with Super-resolution Microscopy

    Science.gov (United States)

    Penwell, Samuel; Ginsberg, Lucas; Noriega Manez, Rodrigo; Ginsberg, Naomi

    2015-03-01

    Conjugated polymers are highly tunable organic semiconductors, which can be solution processed to form thin films, making them prime candidates for organic photovoltaic devices. One of the most important parameters in a conjugated polymer solar cell is the exciton diffusion length, which depends on intermolecular couplings, and is typically on the order of 10 nm. This mean exciton migration can vary dramatically between films and within a single film due to heterogeneities in morphology on length scales of 10's to 100's nm. To study the variability of exciton diffusion and morphology within individual conjugated polymer films, we are adapting stimulated emission depletion microscopy. STED is typically used in biology with well-engineered fluorescent labels or on NV-centers in diamond. I will, however, describe how we have demonstrated STED in conjugated polymer films of MEH-PPV and CN-PPV by taking care to first understand the film's photophysical properties. This new approach provides a way to study exciton diffusion by utilizing subdiffraction optical excitation volumes. In this way, we will obtain a spatiotemporal map of exciton distributions that will help to correlate the energetic landscape to film morphology at the nanoscale. This research is supported in part by the Department of Energy Office of Science Graduate Fellowship Program (DOE SCGF), made possible in part by the American Recovery and Reinvestment Act of 2009, administered by ORISE-ORAU under Contract No. DE-AC05-06.

  16. Click-chemistry approaches to π-conjugated polymers for organic electronics applications

    Science.gov (United States)

    Facchetti, Antonio; Lanari, Daniela; Santoro, Stefano

    2016-01-01

    Given the wide utility of click-chemistry reactions for the preparation of simple moieties within large architecturally complex materials, this minireview article aims at surveying papers exploring their scope in the area of π-conjugated polymers for application in organic electronics to enable advanced functional properties. PMID:28567241

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

    NARCIS (Netherlands)

    Hummelen, JC; Knol, J; Sanchez, L; Kafafi, ZH

    2000-01-01

    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

  18. Visible light induced fast synthesis of protein-polymer conjugates: controllable polymerization and protein activity.

    Science.gov (United States)

    Li, Xin; Wang, Lei; Chen, Gaojian; Haddleton, David M; Chen, Hong

    2014-06-21

    Herein visible light is used to induce RAFT polymerization from protein for preparing protein-polymer conjugates at ambient temperature. Polymerization is fast and can be conveniently controlled with irradiation time. By site-specific polymerization of NIPAm to protein, the protein activity is maintained and in certain cases it presents an efficient on-off-switchable property.

  19. Mechanically strong, fluorescent hydrogels from zwitterionic, fully π-conjugated polymers.

    Science.gov (United States)

    Elmalem, Einat; Biedermann, Frank; Scherer, Maik R J; Koutsioubas, Alexandros; Toprakcioglu, Chris; Biffi, Giulia; Huck, Wilhelm T S

    2014-08-18

    Mechanically strong supramolecular hydrogels (up to 98.9% water content) were obtained by the combination of a rigid, fully π-conjugated polymer backbone and zwitterionic side chains. The gels were characterized by SAXS, SEM and rheology measurements and are fluorescent, stimuli responsive (temperature, salts) and bind DNA.

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

    NARCIS (Netherlands)

    Muszanska, Agnieszka K.; Busscher, Henk J.; Herrmann, Andreas; van der Mei, Henny C.; Norde, Willem

    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

  1. Conjugated polymer-wrapped carbon nanotubes : physical properties and device applications

    NARCIS (Netherlands)

    Gomulya, Widianta; Gao, Jia; Loi, Maria Antonietta

    2013-01-01

    The aim of this article is to present an overview about the preparation method and physical properties of a new hybrid system consisting of single-walled carbon nanotubes (SWNTs) wrapped by conjugated polymers. The technique firstly demonstrated in 2007 has attracted great interest because of the

  2. Sugar–derived organogels as templates for structured, photoluminescent conjugated polymer-inorganic hybrid materials

    OpenAIRE

    Marr, Patricia C.; McBride, Katherine; Evans, Rachel C.

    2013-01-01

    Co-assembly of an inorganic–organic hybrid material through the combination of supramolecular organogel self-assembly, phase partitioning of a conjugated polymer (CP) and transcription of an inorganic oxide leads to a hybrid material with structured domains of organogel, CP and silica within tube and rod microstructures.

  3. Sugar-derived organogels as templates for structured, photoluminescent conjugated polymer-inorganic hybrid materials.

    Science.gov (United States)

    Marr, Patricia C; McBride, Katherine; Evans, Rachel C

    2013-07-14

    Co-assembly of an inorganic-organic hybrid material through the combination of supramolecular organogel self-assembly, phase partitioning of a conjugated polymer (CP) and transcription of an inorganic oxide leads to a hybrid material with structured domains of organogel, CP and silica within tube and rod microstructures.

  4. Characterization of large area flexible plastic solar cells based on conjugated polymer/fullerene composites

    NARCIS (Netherlands)

    Gebeyehu, Desta; Padinger, F.; Brabec, C.J.; Fromherz, T.; Hummelen, J.C.; Sariciftci, N.S.

    1999-01-01

    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. Organic solar cells must fulfill the criteria of stability, efficiency and reduction of production costs to find

  5. Anisotropic conjugated polymer chain conformation tailors the energy migration in nanofibers

    CERN Document Server

    Camposeo, Andrea; Moffa, Maria; Fasano, Vito; Altamura, Davide; Giannini, Cinzia; Pisignano, Dario; Scholes, Gregory D

    2016-01-01

    Conjugated polymers are complex multi-chromophore systems, with emission properties strongly dependent on the electronic energy transfer through active sub-units. Although the packing of the conjugated chains in the solid state is known to be a key factor to tailor the electronic energy transfer and the resulting optical properties, most of the current solution-based processing methods do not allow for effectively controlling the molecular order, thus making the full unveiling of energy transfer mechanisms very complex. Here we report on conjugated polymer fibers with tailored internal molecular order, leading to a significant enhancement of the emission quantum yield. Steady state and femtosecond time-resolved polarized spectroscopies evidence that excitation is directed toward those chromophores oriented along the fiber axis, on a typical timescale of picoseconds. These aligned and more extended chromophores, resulting from the high stretching rate and electric field applied during the fiber spinning proces...

  6. Preparations and properties of anti-corrosion additives of water-soluble metal working fluids for aluminum alloy materials.

    Science.gov (United States)

    Watanabe, Shoji

    2008-01-01

    This short review describes various types of anti-corrosion additives of water-soluble metal working fluids for aluminum alloy materials. It is concerned with synthetic additives classified according to their functional groups; silicone compounds, carboxylic acids and dibasic acids, esters, Diels-Alder adducts, various polymers, nitrogen compounds, phosphoric esters, phosphonic acids, and others. Testing methods for water-soluble metal working fluids for aluminum alloy materials are described for a practical application in a laboratory.

  7. Experimental investigations into the physics of light emitting conjugated polymers

    CERN Document Server

    Whitelegg, S A

    2001-01-01

    chloroprecursor MEH-PPV in-situ of ITO results in a reaction of the polymer with ITO, which significantly shift the emission to high energies. Electroabsorption spectroscopy is used to probe the internal electric fields within operating polymer light emitting devices. When a PPV based LED in an oxygen/water atmosphere, degradation of the device occurs whereby an electric field develops, which opposes the applied electric field. This opposing electric field subsequently decays when the device is turned to its off state. Operating lifetimes and emission efficiencies of polymer light emitting devices are now approaching values suitable for the manufacture and sale of polymer light emitting based products. However, degradation and device performance still continues to be of chief concern and in order for these to be improved the underlying physical processes have to be identified. This thesis aims to identify some of these processes. An investigation in to the optical absorption and emission properties of insolub...

  8. Alkene metathesis - a tool for the synthesis of conjugated polymers.

    Science.gov (United States)

    Bunz, Uwe H F; Mäker, Dominic; Porz, Michael

    2012-05-29

    Alkene metathesis is a superb methodology. We report the progress using alkene metathesis in the synthesis of polymeric organic semiconductors. Three classes of polymers have been synthesized using acyclic diene metathesis (ADMET) or ring opening metathesis polymerization (ROMP), viz., poly(acetylene)s (PA), poly(arylene-vinylene)s (PAV), and organometallic polymers. For PAs, ROMP of cyclooctatetraenes is best, whereas for PAV, both ADMET and indirect and direct ROMP are viable. Metathesis performs flawlessly with the correct monomers, as molybdenum and particularly the robust Ru carbenes demonstrate. When performing ROMP, one is often rewarded with structurally uniform polymers that can display very low polydispersities. Overall, metathesis is a powerful tool for the preparation of semiconducting polymers. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. Electrochemical route to fabricate film-like conjugated microporous polymers and application for organic electronics.

    Science.gov (United States)

    Gu, Cheng; Chen, Youchun; Zhang, Zhongbo; Xue, Shanfeng; Sun, Shuheng; Zhang, Kai; Zhong, Chengmei; Zhang, Huanhuan; Pan, Yuyu; Lv, Ying; Yang, Yanqin; Li, Fenghong; Zhang, Suobo; Huang, Fei; Ma, Yuguang

    2013-07-05

    Film-like conjugated microporous polymers (CMPs) are fabricated by the novel strategy of carbazole-based electropolymerization. The CMP film storing a mass of counterions acting as an anode interlayer provides a significant power-conversion efficiency of 7.56% in polymer solar cells and 20.7 cd A(-1) in polymer light-emitting diodes, demonstrating its universality and potential as an electrode interlayer in organic electronics. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. 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...... and the complex was adsorbed onto the surface before evaporation of gold electrodes. Alternative devices were obtained by spincoating of the polymer solution onto PEDOT:PSS covered indium-doped tin oxide substrates. PEC solar cells gave the best results and the main finding was that the polymer chain served...

  11. Energy transfer from conjugated polymer to bacterial light-harvesting complex

    Science.gov (United States)

    Buczynska, D.; Bujak, Ł.; Loi, M. A.; Brotosudarmo, T. H. P.; Cogdell, R.; Mackowski, S.

    2012-10-01

    Energy transfer from a conjugated polymer blend (poly(9,9-dioctylfluorenyl-2,7-diyl):poly (2-methoxy-5-(2-ethylhexyloxy)-1, 4-phenylenevinylene) to a light-harvesting complex 2 from purple bacteria has been demonstrated using time-resolved fluorescence spectroscopy. For our hybrid nanostructure, we observe a 30% reduction of the fluorescence lifetime of the polymer emission as compared to the pure polymer layer. This result is an important step towards integrating naturally evolved biomolecules with synthetic materials into biohybrid organic electronic systems.

  12. Recent developments in the selective dispersion of single-walled carbon nanotubes using conjugated polymers.

    Science.gov (United States)

    Fong, Darryl; Adronov, Alex

    2017-11-01

    A significant barrier that impedes the commercialization of single-walled carbon nanotube-related applications is that all known synthetic methods produce a complicated mixture of semiconducting and metallic species. For device applications, pure semiconducting or pure metallic samples are desirable. Thus far, the purification methods that have been identified are capable of separating individual carbon nanotube species on a microgram scale, but purification on a large scale has remained elusive. The use of conjugated polymers to selectively disperse specific nanotube species is a promising approach to resolve the scalability issue, but a comprehensive understanding of the selectivity mechanism has not yet been achieved. Here, several of the trends reported in the literature are outlined to further the rational design of conjugated polymers for nanotube sorting. Numerous variables influence dispersion selectivity, including polymer structure and molecular weight, nanotube type used, sonication temperature, amount of polymer relative to nanotube, and solvent. We have organized these seemingly disparate parameters into two simple categories: conjugated polymer structure, and dispersion preparation conditions. Most importantly, we consider the mechanistic arguments that have been proposed, and provide additional insights based on the observations in the literature.

  13. 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.

  14. 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...

  15. 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)

  16. 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.

  17. Water-soluble titanium alkoxide material

    Science.gov (United States)

    Boyle, Timothy J.

    2010-06-22

    A water soluble, water stable, titanium alkoxide composition represented by the chemical formula (OC.sub.6H.sub.6N).sub.2Ti(OC.sub.6H.sub.2(CH.sub.2N(CH.sub.3).sub.2).sub- .3-2,4,6).sub.2 with a theoretical molecular weight of 792.8 and an elemental composition of 63.6% C, 8.1% H, 14.1% N, 8.1% O and 6.0% Ti.

  18. A Typical Metal-Ion-Responsive Color-Tunable Emitting Insulated π-Conjugated Polymer Film.

    Science.gov (United States)

    Hosomi, Takuro; Masai, Hiroshi; Fujihara, Tetsuaki; Tsuji, Yasushi; Terao, Jun

    2016-10-17

    We report the synthesis of an insulated π-conjugated polymer containing 2,2'-bipyridine moieties as metal coordination sites. Metal coordination to the polymer enabled easy and reversible tuning of the luminescent color without changes to the main chain skeleton. The permethylated α-cyclodextrin (PM α-CD)-based insulation structure allowed the metalated polymers to demonstrate efficient emission even in the solid state, with identical spectral shapes to the dilute solutions. In addition, the coordination ability of the metal-free polymer was maintained in the solid state, resulting in reversible changes in the luminescent color in response to the metal ions. The synthesized polymer is expected to be suitable for application in recyclable luminescent sensors to distinguish different metal ions. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. Thiophene-based donor-acceptor conjugated polymer as potential ...

    Indian Academy of Sciences (India)

    Polymer light-emitting diodes are fabricated using PTh-CN as the emissive layer with a device configuration of ITO/PEDOT:PSS/PTh-CN/Al. The device showed stable saturated red electroluminescence with CIE coordinate values (0.65, 0.32) at 12 V, which are very close to the values for standard red demanded by the ...

  20. Exciton diffusion and dissociation in conjugated polymer/fullerene heterostructures

    NARCIS (Netherlands)

    Markov, D.E.; Amsterdam, E.; Blom, P.W.M.; Sieval, A.B.; Hummelen, J.C.; Heremans, PL; Muccini, M; Hofstraat, H

    2004-01-01

    Time-resolved luminescence spectroscopy has been used to investigate exciton diffusion in thin films of poly(p-phenylene vinylene) (PPV) based derivatives. Exciton density distribution upon photoexcitation in polymer/fullerene heterostructures has been modeled and exciton diffusion length values of

  1. Magnetic field effect in highly pure, highly fluorescent conjugated polymers

    Energy Technology Data Exchange (ETDEWEB)

    Graupner, W.; Sacher, M.; Graupner, M.; Zenz, C.; Grampp, G.; Hermetter, A.; Leising, G.

    1998-07-01

    The authors report on the magnetic field effect (MFE) on the photoluminescence in films of a highly fluorescent conjugated laddertype poly(paraphenylene) (LPPP). They observe no MFE for the pure material, however, the introduction of a very small content of chemical defects via photo-oxidation leads to a MFE proportional to the amount of defects. The chemically induced increase in MFE is correlated with a change in other properties of the LPPP films, such as photoluminescence emission and excitation spectra, transient photoluminescence and infrared spectra.

  2. Truxene-Based Hyperbranched Conjugated Polymers: Fluorescent Micelles Detect Explosives in Water.

    Science.gov (United States)

    Huang, Wei; Smarsly, Emanuel; Han, Jinsong; Bender, Markus; Seehafer, Kai; Wacker, Irene; Schröder, Rasmus R; Bunz, Uwe H F

    2017-01-25

    We report two hyperbranched conjugated polymers (HCP) with truxene units as core and 1,4-didodecyl-2,5-diethynylbenzene as well as 1,4-bis(dodecyloxy)-2,5-diethynylbenzene as comonomers. Two analogous poly(para-phenyleneethynylene)s (PPE) are also prepared as comparison to demonstrate the difference between the truxene and the phenyl moieties in their optical properties and their sensing performance. The four polymers are tested for nitroaromatic analytes and display different fluorescence quenching responses. The quenching efficiencies are dependent upon the spectral overlap between the absorbance of the analyte and the emission of the fluorescent polymer. Optical fingerprints are obtained, based on the unique response patterns of the analytes toward the polymers. With this small sensor array, one can distinguish nine nitroaromatic analytes with 100% accuracy. The amphiphilic polymer F127 (a polyethylene glycol-polypropylene glycol block copolymer) carries the hydrophobic HCPs and self-assembles into micelles in water, forming highly fluorescent HCP micelles. The micelle-bound conjugated polymers detect nitroaromatic analytes effectively in water and show an increased sensitivity compared to the sensing of nitroaromatics in organic solvents. The nitroarenes are also discriminated in water using this four-element chemical tongue.

  3. Conjugation of Polymer-Coated Gold Nanoparticles with Antibodies—Synthesis and Characterization

    Directory of Open Access Journals (Sweden)

    Gamze Tan

    2015-08-01

    Full Text Available The synthesis of polymer-coated gold nanoparticles with high colloidal stability is described, together with appropriate characterization techniques concerning the colloidal properties of the nanoparticles. Antibodies against vascular endothelial growth factor (VEGF are conjugated to the surface of the nanoparticles. Antibody attachment is probed by different techniques, giving a guideline about the characterization of such conjugates. The effect of the nanoparticles on human adenocarcinoma alveolar basal epithelial cells (A549 and human umbilical vein endothelial cells (HUVECs is probed in terms of internalization and viability assays.

  4. Correlating structure with fluorescence emission in phase-separated conjugated-polymer blends.

    Science.gov (United States)

    Chappell, John; Lidzey, David G; Jukes, Paul C; Higgins, Anthony M; Thompson, Richard L; O'Connor, Stephen; Grizzi, Ilaria; Fletcher, Robert; O'Brien, Jim; Geoghegan, Mark; Jones, Richard A L

    2003-09-01

    Blends of conjugated polymers are frequently used as the active semiconducting layer in light-emitting diodes and photovoltaic devices. Here we report the use of scanning near-field optical microscopy, scanning force microscopy and nuclear-reaction analysis to study the structure of a thin film of a phase-separated blend of two conjugated polymers prepared by spin-casting. We show that in addition to the well-known micrometre-scale phase-separated morphology of the blend, one of the polymers preferentially wets the surface and forms a 10-nm-thick, partially crystallized wetting layer. Using near-field microscopy we identify unexpected changes in the fluorescence emission from the blend that occurs in a 300-nm-wide band located at the interface between the different phase-separated domains. Our measurements provide an insight into the complex structure of phase-separated conjugated-polymer thin films. Characterizing and controlling the properties of the interfaces in such films will be critical in the further development of efficient optoelectronic devices.

  5. Conjugated polymers/semiconductor nanocrystals hybrid materials--preparation, electrical transport properties and applications.

    Science.gov (United States)

    Reiss, Peter; Couderc, Elsa; De Girolamo, Julia; Pron, Adam

    2011-02-01

    This critical review discusses specific preparation and characterization methods applied to hybrid materials consisting of π-conjugated polymers (or oligomers) and semiconductor nanocrystals. These materials are of great importance in the quickly growing field of hybrid organic/inorganic electronics since they can serve as active components of photovoltaic cells, light emitting diodes, photodetectors and other devices. The electronic energy levels of the organic and inorganic components of the hybrid can be tuned individually and thin hybrid films can be processed using low cost solution based techniques. However, the interface between the hybrid components and the morphology of the hybrid directly influences the generation, separation and transport of charge carriers and those parameters are not easy to control. Therefore a large variety of different approaches for assembling the building blocks--conjugated polymers and semiconductor nanocrystals--has been developed. They range from their simple blending through various grafting procedures to methods exploiting specific non-covalent interactions between both components, induced by their tailor-made functionalization. In the first part of this review, we discuss the preparation of the building blocks (nanocrystals and polymers) and the strategies for their assembly into hybrid materials' thin films. In the second part, we focus on the charge carriers' generation and their transport within the hybrids. Finally, we summarize the performances of solar cells using conjugated polymer/semiconductor nanocrystals hybrids and give perspectives for future developments.

  6. 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.

  7. π-Conjugated Microporous Polymer Films: Designed Synthesis, Conducting Properties, and Photoenergy Conversions.

    Science.gov (United States)

    Gu, Cheng; Huang, Ning; Chen, Youchun; Qin, Leiqiang; Xu, Hong; Zhang, Shitong; Li, Fenghong; Ma, Yuguang; Jiang, Donglin

    2015-11-09

    Conjugated microporous polymers are a unique class of polymers that combine extended π-conjugation with inherent porosity. However, these polymers are synthesized through solution-phase reactions to yield insoluble and unprocessable solids, which preclude not only the evaluation of their conducting properties but also the fabrication of thin films for device implementation. Here, we report a strategy for the synthesis of thin films of π-conjugated microporous polymers by designing thiophene-based electropolymerization at the solution-electrode interface. High-quality films are prepared on a large area of various electrodes, the film thickness is controllable, and the films are used for device fabrication. These films are outstanding hole conductors and, upon incorporation of fullerenes into the pores, function as highly efficient photoactive layers for energy conversions. Our film strategy may boost the applications in photocatalysis, energy storage, and optoelectronics. © 2015 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA. This is an open access article under the terms of the Creative Commons Attribution Non-Commercial License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited and is not used for commercial purposes.

  8. Conjugated Microporous Polymer Nanosheets for Overall Water Splitting Using Visible Light.

    Science.gov (United States)

    Wang, Lei; Wan, Yangyang; Ding, Yanjun; Wu, Sikai; Zhang, Ying; Zhang, Xinlei; Zhang, Guoqing; Xiong, Yujie; Wu, Xiaojun; Yang, Jinlong; Xu, Hangxun

    2017-10-01

    Direct water splitting into H2 and O2 using photocatalysts by harnessing sunlight is very appealing to produce storable chemical fuels. Conjugated polymers, which have tunable molecular structures and optoelectronic properties, are promising alternatives to inorganic semiconductors for water splitting. Unfortunately, conjugated polymers that are able to efficiently split pure water under visible light (400 nm) via a four-electron pathway have not been previously reported. This study demonstrates that 1,3-diyne-linked conjugated microporous polymer nanosheets (CMPNs) prepared by oxidative coupling of terminal alkynes such as 1,3,5-tris-(4-ethynylphenyl)-benzene (TEPB) and 1,3,5-triethynylbenzene (TEB) can act as highly efficient photocatalysts for splitting pure water (pH ≈ 7) into stoichiometric amounts of H2 and O2 under visible light. The apparent quantum efficiencies at 420 nm are 10.3% and 7.6% for CMPNs synthesized from TEPB and TEB, respectively; the measured solar-to-hydrogen conversion efficiency using the full solar spectrum can reach 0.6%, surpassing photosynthetic plants in converting solar energy to biomass (globally average ≈0.10%). First-principles calculations reveal that photocatalytic H2 and O2 evolution reactions are energetically feasible for CMPNs under visible light irradiation. The findings suggest that organic polymers hold great potential for stable and scalable solar-fuel generation. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. Watching the coherent birth of polaron pairs in conjugated polymers

    OpenAIRE

    De Sio, Antonietta; Troiani, Filippo; Maiuri, Margherita; Réhault, Julien; Sommer, Ephraim; Lim, James; Huelga, Susana F.; Plenio, Martin B.; Rozzi, Carlo Andrea; Cerullo, Giulio; Molinari, Elisa; Lienau, Christoph

    2016-01-01

    Organic semiconductors have the remarkable property that their optical excitation not only generates charge-neutral electron-hole pairs (excitons) but also charge-separated polaron pairs with high yield. The microscopic mechanisms underlying this charge separation have been debated for many years. Here we use ultrafast two-dimensional electronic spectroscopy to study the dynamics of polaron pair formation in a prototypical polymer thin film on a sub-20-fs time scale. We observe multi-period p...

  10. 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: Polymer science (UMCH-V) Impact factor: 6.259, year: 2016

  11. 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...... 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....

  12. Novel enzyme-polymer conjugates for biotechnological applications

    Directory of Open Access Journals (Sweden)

    Oscar Romero

    2013-02-01

    Full Text Available In the present research, a rapid, simple and efficient chemoselective method for the site-directed incorporation of tailor-made polymers into protein to create biocatalysts with excellent properties for pharmaceutical industrial purpose has been performed. First we focused on the protein engineering of the Geobacillus thermocatenulatus lipase 2 (BTL2 to replace the two cysteines (Cys65, Cys296 in the wild type enzyme (BTL-WT by two serines. Then, by similar mode, a unique cysteine was introduced in the lid area of the protein. For the site-directed polymer incorporation, a set of different tailor-made thiol-ionic-polymers were synthesized and the protein cysteine was previously activated with 2,2-dithiodipyridine (2-PDS to allow the disulfide exchange. The protected BTL variants were specifically modified with the different polymers in excellent yields, creating a small library of new biocatalysts. Different and important changes in the catalytic properties, possible caused by structural changes in the lid region, were observed. The different modified biocatalysts were tested in the synthesis of intermediates of antiviral and antitumor drugs, like nucleoside analogues and derivatives of phenylglutaric acid. In the hydrolysis of per-acetylated thymidine, the best biocatalyst was the BTL*-193-DextCOOH , where the activity was increased in 3-fold and the regioselectivity was improved, reaching a yield of 92% of 3’-O-acetyl-thymidine. In the case of the asymmetric hydrolysis of dimethyl phenylglutarate, the best result was found with BTL*-193-DextNH2-6000, where the enzyme activity was increased more than 5-fold and the enantiomeric excess was >99%.

  13. 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

  14. 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

    OpenAIRE

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

    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) (...

  15. 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.

  16. 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.

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

    Science.gov (United States)

    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. PMID:28788568

  18. Polaron effects and electric field dependence of the charge carrier mobility in conjugated polymers.

    Science.gov (United States)

    Jakobsson, Mattias; Stafström, Sven

    2011-10-07

    Charge transport in conjugated polymers has been investigated using Monte Carlo simulations implemented on top of the Marcus theory for donor-acceptor transition rates. In particular, polaron effects and the dependency of the mobility on the temperature and the applied electric field have been studied. The conclusions are that while the qualitative temperature dependence is similar to that predicted by Miller-Abrahams theory in the Gaussian disorder model (GDM), the electric field dependence is characterized by a crossover into the Marcus inverted region, not present in the GDM. Furthermore, available analytical approximations to describe the electric field dependence of the mobility in Marcus theory fail to fit the simulation data and hence cannot be used to directly draw conclusions about the importance of polaron effects for charge transport in conjugated polymers. © 2011 American Institute of Physics

  19. 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.

  20. 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.

  1. A Luminescent Hypercrosslinked Conjugated Microporous Polymer for Efficient Removal and Detection of Mercury Ions.

    Science.gov (United States)

    Xiang, Lu; Zhu, Yunlong; Gu, Shuai; Chen, Dongyang; Fu, Xian; Zhang, Yindong; Yu, Guipeng; Pan, Chunyue; Hu, Yuehua

    2015-09-01

    A hypercrosslinked conjugated microporous polymer (HCMP-1) with a robustly efficient absorption and highly specific sensitivity to mercury ions (Hg(2+)) is synthesized in a one-step Friedel-Crafts alkylation of cost-effective 2,4,6-trichloro-1,3,5-triazine and dibenzofuran in 1,2-dichloroethane. HCMP-1 has a moderate Brunauer-Emmett-Teller specific surface (432 m(2) g(-1)), but it displays a high adsorption affinity (604 mg g(-1)) and excellent trace efficiency for Hg(2+). The π-π* electronic transition among the aromatic heterocyclic rings endows HCMP-1 a strong fluorescent property and the fluorescence is obviously weakened after Hg(2+) uptake, which makes the hypercrosslinked conjugated microporous polymer a promising fluorescent probe for Hg(2+) detection, owning a super-high sensitivity (detection limit 5 × 10(-8) mol L(-1)). © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. Hydrogen-bonded supramolecular conjugated polymer nanoparticles for white light-emitting devices.

    Science.gov (United States)

    Lin, Jin-Yi; Wong, JenIt; Xie, Ling-Hai; Dong, Xiao-Chen; Yang, Hui Ying; Huang, Wei

    2014-05-01

    Supramolecular polyfluorenol enable assembly into conjugated polymer nanoparticles (CPNs). Poly{9-[4-(octyloxy)phenyl]fluoren-9-ol-2,7-diyl} (PPFOH)-based supramolecular nanoparticles are prepared via reprecipitation. PPFOH nanoparticles with diameters ranging from 40 to 200 nm are obtained by adding different amounts of water into DMF solution. Size-dependent luminescence is observed in PPFOH-based hydrogen-bonded nanoparticles that is different from that of poly(9,9-dioctylfluorenes). Finally, white light-emitting devices using CPNs with a size of 80 nm exhibit white emission with the CIE coordinates (0.31, 0.34). Amphiphilic conjugated polymer nanoparticles are potential organic nano-inks for the fabrication of organic devices in printed electronics. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. One-Dimensional Metals Conjugated Polymers, Organic Crystals, Carbon Nanotubes

    CERN Document Server

    Roth, Siegmar

    2004-01-01

    Low-dimensional solids are of fundamental interest in materials science due to their anisotropic properties. Written not only for experts in the field, this book explains the important concepts behind their physics and surveys the most interesting one-dimensional systems and discusses their present and emerging applications in molecular scale electronics. The second edition of this successful book has been completely revised to include the remarkable achievements of the last ten years of research and applications. Chemists, polymer and materials scientists as well as students will find this bo

  4. 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

  5. Particle-in-a-bos model of one-dimensional excitons in conjugated polymers

    DEFF Research Database (Denmark)

    Pedersen, T.G.; Johansen, P.M.; Pedersen, H.C.

    2000-01-01

    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...... 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....

  6. 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...

  7. New Type of Donor-Acceptor Through-Space Conjugated Polymer

    Directory of Open Access Journals (Sweden)

    Lin Lin

    2010-01-01

    Full Text Available We report the synthesis and properties of a novel through-space conjugated polymer with a [2.2]paracyclophane skeleton. The obtained polymer possessed donor (fluorene and acceptor (2,1,3-benzothiadiazole segments that were alternately π-stacked in proximity via the [2.2]paracyclophane moieties. The good overlap between the emission peak of the donor unit (fluorene and the CT band of the acceptor unit (2,1,3-benzothiadiazole caused fluorescence resonance energy transfer, and the visible green light emission from the acceptor unit was observed.

  8. One-Pot Synthesis of Thermoresponsive Amyloidogenic Peptide-Polymer Conjugates via Thio-Bromo "Click" Reaction of RAFT Polymers.

    Science.gov (United States)

    Kumar, Sonu; Deike, Stefanie; Binder, Wolfgang H

    2018-01-01

    A synthetic strategy to efficiently prepare main-chain peptide-polymer conjugates probing their aggregation in solution is described. An in situ tandem reaction based on aminolysis/thio-bromo "click" reaction is performed to tether an amyloidogenic peptide fragment amyloid-β17-20 (Leu-Val-Phe-Phe (LVFF)) to the ω-chain end of poly(diethylene glycol methyl ether acrylate) (PDEGA), prepared via reversible addition fragmentation chain transfer polymerization. Structural confirmation of the constructed conjugates PDEGA-LVFF (Mn,SEC = 5600, Ð = 1.21), (Mn,SEC = 7600, Ð = 1.16), and (Mn,SEC = 8900, Ð = 1.15) is successfully made by combined studies of 1 H NMR, size-exclusion chromatography, matrix-assisted laser desorption ionization time-of-flight (MALDI-TOF) mass spectrometry, and electrospray ionization time-of-flight (ESI-TOF) mass spectrometry. The effect of the peptidic constituent on the thermoresponsive behavior of the polymer is examined by UV-vis spectroscopy, and the self-assembly behavior of the amphiphilic conjugate is further exploited, exhibiting micellar morphology in aqueous solution. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. Enhanced Reciprocal Interactions between Molecular Stresses and Optoelectronic Energy Transfers for High Efficiency Long Life Devices Based on Conjugated Polymers

    Science.gov (United States)

    2014-10-15

    Molecular Stresses and Optoelectronic Energy Transfers for High Efficiency Long Life Devices Based on Conjugated Polymers 5a. CONTRACT NUMBER FA2386-13...14. ABSTRACT This report describes an investigation into the effects of mechanical deformation on photoluminescence (PL) behavior for the neat...conjugated polymers : poly[2-methoxy-5-(2-ethylhexyloxy)-1,4-phenylenevinylene] (MEH-PPV) and polythiophenes (P3HT, P3BT, P3EHT). This study used a

  10. Silica core/conjugated polymer shell particles via seeded Knoevenagel dispersion polymerization - laser action in whispering gallery mode resonators.

    Science.gov (United States)

    Ciftci, Sibel; Mikosch, Annabel; Haehnle, Bastian; Witczak, Łukasz; Kuehne, Alexander J C

    2016-12-06

    Here, we present a seeded Knoevenagel dispersion polymerization to generate hybrid particles with a conjugated polymer shell on inorganic silica cores. This seeded dispersion polymerization facilitates the generation of core-shell particles, which exhibit whispering gallery mode lasing. The lasing threshold decreases while the spectral range of emission increases with increasing shell thickness. This novel seeded Knoevenagel dispersion polymerization opens up a facile and metal free pathway towards single particle conjugated polymer lasers on the micrometer scale.

  11. Graphene oxide-cationic polymer conjugates: Synthesis and application as gene delivery vectors.

    Science.gov (United States)

    Teimouri, Mohsen; Nia, Azadeh Hashem; Abnous, Khalil; Eshghi, Hossein; Ramezani, Mohammad

    2016-01-01

    Nanomedicine as the interface between nanotechnology and medical sciences is a new area that has attracted the attention of vast groups of researchers. Carbon nanomaterials are common platform for synthesis of nanoparticles for biomedical applications due to their low cytotoxicity and feasible internalization into mammalian cell lines (Yang et al., 2007; Arora et al., 2014; Oh and Park, 2014). Synthesis of vectors based on various cationic polymers polyethylenimine (PEI), polypropylenimine (PPI) and polyamidoamine (PAMAM) and their derivatives were considered as a strategy for transferring plasmid DNA and treatment of genetic diseases. Considering the low cytotoxicity of graphene, chemical modification of its surface has led to fabrication of novel gene delivery systems based on graphene and graphene oxide. Herein we report the synthesis of three groups of vectors based on conjugation of graphene oxide (GO) with alkylated derivatives of three different cationic polymers (polyethylenimine (PEI), polypropylenimine (PPI) and polyamidoamine (PAMAM)) through different linkers including surface carboxyl group, glycine and spermidine. Two main challenges in design of gene delivery vectors is decreasing cytotoxicity while improving the transfection efficiency. All synthesized vectors showed significantly lower cellular toxicity compared to bare polymer. A plasmid encoding green fluorescent protein (GFP) was used to evaluate the transfection efficiency of nanoparticles both qualitatively using live cell fluorescent imaging and quantitatively using flow cytometry and each vector was compared to its polymer base. Most successful conjugation strategy was observed in the case of PEI conjugates among which most efficient vector was PEI-GO conjugate bearing glycine linker. This vector was 9 fold more effective in terms of the percent of EGFP transfected cells. Copyright © 2016 Elsevier B.V. All rights reserved.

  12. Measuring Exciton Migration in Conjugated Polymer Films with Ultrafast Time Resolved Stimulated Emission Depletion Microscopy

    Science.gov (United States)

    Penwell, Samuel

    Conjugated polymers are highly tunable organic semiconductors, which can be solution processed to form thin films, making them prime candidates for organic photovoltaic devices. One of the most important parameters in a conjugated polymer solar cell is the exciton diffusion length, which depends on intermolecular couplings, and is typically on the order of 10 nm. This mean exciton migration can vary dramatically between films and within a single film due to heterogeneities in morphology on length scales of 10's to 100's nm. To study the variability of exciton diffusion and morphology within individual conjugated polymer films, we are adapting stimulated emission depletion (STED) microscopy. STED is typically used in biology with sparse well-engineered fluorescent labels or on NV-centers in diamond. I will, however, describe how we have demonstrated the extension of STED to conjugated polymer films and nanoparticles of MEH-PPV and CN-PPV, despite the presence of two photon absorption, by taking care to first understand the material's photophysical properties. We then further adapt this approach, by introducing a second ultrafast STED pulse at a variable delay. Excitons that migrate away from the initial subdiffraction excitation volume during the ps-ns time delay, are preferentially quenched by the second STED pulse, while those that remain in the initial volume survive. The resulting effect of the second STED pulse is modulated by the degree of migration over the ultrafast time delay, thus providing a new method to study exciton migration. Since this technique utilizes subdiffraction optical excitation and detection volumes with ultrafast time resolution, it provides a means of spatially and temporally resolving measurements of exciton migration on the native length and time scales. In this way, we will obtain a spatiotemporal map of exciton distributions and migration that will help to correlate the energetic landscape to film morphology at the nanoscale.

  13. Optically detected magnetic resonance studies on π-conjugate polymers and novel carbon allotropes

    Energy Technology Data Exchange (ETDEWEB)

    Partee, Jonathan [Iowa State Univ., Ames, IA (United States)

    1999-02-12

    This report describes the following: introduction to photoluminescence detected magnetic resonance (PLDMR); introduction to π-conjugated systems; PLDMR measurements on poly(p-phenylene)-type ladder polymers; PLMDR measurements on poly(p-phenylene ethylene); and PLDMR measurements on C70, polythiophene, poly(p-phenylene vinylene) and Dan-40. Appendices to this report describe: Operation of ODMR (optically detected magnetic resonance) spectrometer; ODMR system parameters; and Special purpose circuitry.

  14. Ionic two photon states and optical nonlinearity in. pi. -conjugated polymers

    Energy Technology Data Exchange (ETDEWEB)

    Dixit, S.N. (Lawrence Livermore National Lab., CA (USA)); Guo, D.; Mazumdar, S. (Arizona Univ., Tucson, AZ (USA). Dept. of Physics)

    1990-11-06

    A microscopic mechanism of optical nonlinearity in {pi}-conjugated polymers is presented. It is shown that the bulk of the nonlinearity is determined by only two well defined channels, even though an infinite number of channels are possible in principle. The above conclusion is true for both short and long range Coulomb interactions. The complete frequency dependence of the third harmonic generation in both trans-polyacetylene and polydiacetylene are explained within the same theoretical picture. 19 refs., 4 figs.

  15. Designing emissive conjugated polymers with small optical gaps: a step towards organic polymeric infrared lasers

    OpenAIRE

    Shukla, Alok; Mazumdar, Sumit

    1999-01-01

    We show that chemical modification of the trans-polyacetylene structure that involves substitution of the backbone hydrogen atoms with conjugated side groups, leads to reduction of the backbone bond alternation as well as screening of the effective Coulomb interaction. Consequently the optical gap of the substituted material is smaller than the parent polyene with the same backbone length, and the excited state ordering is conducive to efficient photoluminescence. The design of organic polyme...

  16. 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

  17. Nitrogen-Rich Conjugated Microporous Polymers: Facile Synthesis, Efficient Gas Storage, and Heterogeneous Catalysis.

    Science.gov (United States)

    Liao, Yaozu; Cheng, Zhonghua; Zuo, Weiwei; Thomas, Arne; Faul, Charl F J

    2017-11-08

    Nitrogen-rich conjugated microporous polymers (NCMPs) have attracted great attention in recent years owing to their polarity, basicity, and ability to coordinate metal ions. Herein, three NCMPs, structurally close to polyaniline, were facilely synthesized via chemical oxidative polymerization between multiconnected aniline precursors. The NCMPs with high N content (11.84 wt %), intrinsic ultramicroporosity (94% activity in Suzuki-Miyaura coupling reactions after six continuous runs.

  18. 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

  19. Tracking the coherent generation of polaron pairs in conjugated polymers.

    Science.gov (United States)

    De Sio, Antonietta; Troiani, Filippo; Maiuri, Margherita; Réhault, Julien; Sommer, Ephraim; Lim, James; Huelga, Susana F; Plenio, Martin B; Rozzi, Carlo Andrea; Cerullo, Giulio; Molinari, Elisa; Lienau, Christoph

    2016-12-08

    The optical excitation of organic semiconductors not only generates charge-neutral electron-hole pairs (excitons), but also charge-separated polaron pairs with high yield. The microscopic mechanisms underlying this charge separation have been debated for many years. Here we use ultrafast two-dimensional electronic spectroscopy to study the dynamics of polaron pair formation in a prototypical polymer thin film on a sub-20-fs time scale. We observe multi-period peak oscillations persisting for up to about 1 ps as distinct signatures of vibronic quantum coherence at room temperature. The measured two-dimensional spectra show pronounced peak splittings revealing that the elementary optical excitations of this polymer are hybridized exciton-polaron-pairs, strongly coupled to a dominant underdamped vibrational mode. Coherent vibronic coupling induces ultrafast polaron pair formation, accelerates the charge separation dynamics and makes it insensitive to disorder. These findings open up new perspectives for tailoring light-to-current conversion in organic materials.

  20. Transition-Metal-Free Synthesis of 1,3-Butadiene-Containing π-Conjugated Polymers.

    Science.gov (United States)

    Cai, Xuediao; Liu, Yating; Lu, Tian; Yang, Rui; Luo, Chuxin; Zhang, Qi; Chai, Yonghai

    2016-12-01

    This work describes the synthesis of π-conjugated polymers possessing arylene and 1,3-butadiene alternating units in the main chain by the reaction of α,β-unsaturated ester/nitrile containing γ-H with aromatic/heteroaromatic aldehyde compound. By using 4-(4-formylphenyl)-2-butylene acid ethyl ester as a model monomer, the different polymerization conditions, including catalyst, catalyst amount, and solvent, are optimized. The polymerization of 4-(4-formylphenyl)-2-butylene acid ethyl ester is carried out by refluxing in ethanol for 72 h with 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) as a catalyst to give a 1,3-butadiene-containing π-conjugated polymer, poly(phenylene-1,3-butadiene), in 84.3% yield with M¯n and M¯w/M¯n (PDI) estimated as 6172 and 1.65, respectively. Based on this new methodology, a series of π-conjugated polymers containing 1,3-butadiene units with different substituents are obtained in high yields. A possible mechanism is proposed for the polymerization through a six-membered ring transition state and then a 1,5-H shift intermediate. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. 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.

  2. Conjugated microporous polymers-based fluorescein for fluorescence detection of 2,4,6-trinitrophenol.

    Science.gov (United States)

    Geng, Tong-Mou; Ye, Sai-Nan; Wang, Yu; Zhu, Hai; Wang, Xie; Liu, Xue

    2017-04-01

    2,4,6-Trinitrophenol (TNP, also called picric acid, PA) pose a large threat to environmental health, public safety and military security. Conjugated microporous polymers are emerging new fluorescence sensing materials for TNP. In this paper, we report the synthesis of two fluorescein containing conjugated microporous polymers (DTF and TTF) through the palladium catalyzed Sonogashira-Hagihara polycondensation reactions of tetraiodofluorescein sodium salt (TIFA) with 1,4-diethynylbenzene (DEB) or 1,3,5-triethynylbenzene (TEB). DTF and TTF are porous with the BET surface areas of 705 and 712m2g-1 and exhibit high chemical and thermal stabilities. The formation of conjugated polymers with the incorporation of ethynyl groups leads to the fluorescent properties. The fluorescence quenching behaviors of DTF by nitroaromatic analytes in THF suspension are investigated. It is found that the fluorescence of DTF can be effectively quenched by 2,4,6-trinitrophenol over 2-nitrophenol (NP), 4-nitrotoluene (NT), nitrobenzene (NB), phenol (PhOH), p-dichlorobenzene (DClB) and 2,4-dinitrotoluene (DNT) with an SV constant of 2.08×103Lmol-1 and a detection limit of 7.22×10-7molL-1 (0.165mgL-1). In short, the DTF may be a new kind of fluorescence sensing material for detecting TNP. Copyright © 2016 Elsevier B.V. All rights reserved.

  3. 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.

  4. Sensitive Conjugated-Polymer-Based Fluorescent ATP Probes and Their Application in Cell Imaging.

    Science.gov (United States)

    Chen, Zhifang; Wu, Pan; Cong, Rong; Xu, Naihan; Tan, Ying; Tan, Chunyan; Jiang, Yuyang

    2016-02-17

    Three cationic conjugated polyelectrolytes (CPEs) with a common poly(p-phenylene ethynylene terthiophene) backbone and side chains of different lengths, named as PPET3-N1, PPET3-N2, and PPET3-N3, were designed and synthesized. The UV-vis absorption and fluorescence spectra of the polymers vary strongly with solvent composition, suggesting that the polymers are strongly aggregated in H2O. In addition, the spectroscopic properties of the polymers are affected by small-molecule ATP, characterized by significant fluorescence intensity decreases and red shifts of their absorption bands. Further application of these polymers in cell imaging was studied by confocal fluorescence microscopy, which demonstrated that all of the polymers were localized on the cell membrane and partially inside of cells and that the staining effect gradually increased with the length of the polymer side chains. On the basis of the low cytotoxicity and efficient quenching of PPET3-N2 by ATP, the dose and time effects of ATP on PPET3-N2 imaging were studied, and the results indicated that this polymer might have potential in cell imaging for ATP semiquantification in vivo.

  5. 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

  6. Development of novel conjugated donor polymers for high-efficiency bulk-heterojunction photovoltaic devices.

    Science.gov (United States)

    Chen, Junwu; Cao, Yong

    2009-11-17

    Solar cells are one attractive method for harnessing inexhaustible clean energy from the sun. Organic photovoltaic technology is emerging as a potential competitor to silicon-based photovoltaic cells (PVCs), and their power conversion efficiencies (PCE) can now exceed 6%. Polymeric bulk-heterojunction (BHJ) PVCs, whose photoactive layer is composed of a blend of bicontinuous and interpenetrating donors and acceptors, can maximize interfacial area between the donor and the acceptor. Classic polymer donors, such as dialkoxy-substituted poly(para-phenylene vinylene)s (PPVs) and poly(3-hexylthiophene) (P3HT), have been widely investigated. However, advances in synthetic methodology provide new avenues for the development of novel conjugated polymer donors with improved power conversion efficiencies. Recently, researchers have achieved great advances in this area. This Account primarily focuses on novel donor polymers that have shown power conversion efficiencies greater than 1%. 2,1,3-Benzothiadiazole, thiophene, thieno[3,4-b]pyrazine, quinoxaline, and silole have emerged as useful heterocycles for constructing a variety of conjugated polymers for photovoltaic applications. We summarize useful information, such as molecular weights, absorption, bandgap, energy levels, and their photovoltaic performances with detailed device parameters (see comparison tables), about these novel donor polymers. We use statistical summaries to evaluate several important parameter relationships among these polymer donors including open-circuit voltage versus HOMO, power conversion efficiency versus bandgap, and power conversion efficiency versus hole mobility. Further statistical analysis of the data listed in these tables may guide further structural design and evaluation of polymer donor materials.

  7. 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.

  8. The effect of fluorine substituents in conjugated polymers

    CERN Document Server

    Loevenich, P W

    2001-01-01

    quantum efficiency of 1.1%. Furthermore, an oligo(p-phenylene vinylene) was synthesised that contained two terminal fluorinated benzene rings and two central non-fluorinated benzene rings, all connected by vinylene bridges. This material aggregated in a 'brickwall' motif, where each molecule overlaps with two halves of molecules in the row above and below. The structure of this J aggregate is due to aryl-fluoroaryl-interactions and was demonstrated by X-ray crystal structure analysis. A new route to a well-defined block copolymer with alternating PEO-solubilising groups and fluorinated distyrylbenzene units was established. The Horner Wittig reaction was used as the polycondensation reaction. The non-fluorinated analogue of this block copolymer was prepared via the Wittig reaction. Both polymers were soluble in chloroform and free-standing films could be cast from solution. The position of the HOMO and LUMO energy levels of these two materials were determined by a combination of cyclic voltammetry, UV photoel...

  9. Uniform polymer-protein conjugate by aqueous AGET ATRP using protein as a macroinitiator.

    Science.gov (United States)

    Zhu, Binbin; Lu, Diannan; Ge, Jun; Liu, Zheng

    2011-05-01

    In situ aqueous activators generated by electron transfer for atom transfer radical polymerization (AGET ATRP) in air, using an enzyme as a macroinitiator, has been proposed to prepare uniform polymer-protein conjugates with improved stability under adverse conditions. In the first step, an initiator, 2-bromoisobutyryl bromide (BIB), was grafted onto the protein surface by reaction with the amino groups. The second step was in situ AGET ATRP polymerization in air using CuBr(2)/1,1,4,7,7-pentamethyldiethylenetriamine as a catalyst and ascorbic acid as a reducing agent. The effectiveness of this method has been demonstrated using horseradish peroxidase (HRP) as a model protein and acrylamide as the monomer, which yielded HRP-polyacrylamide conjugate with a mean particle size of about 20-30 nm. The grafting of BIB onto HRP and the subsequent polymerization yielding a polyacrylamide chain were confirmed by nuclear magnetic resonance and matrix-assisted laser desorption ionization time-of-flight spectrometry analysis. The size of the conjugate was shown to be a function of monomer loading and reaction time. The HRP conjugates yielded essentially retained the catalytic behavior of HRP in free form, as shown by K(m) and V(max) values, but exhibited significantly enhanced thermal stability against high temperature and trypsin digestion. The use of protein as the macroinitiator prevented the formation of copolymer and thus facilitated purification of the protein conjugate. The uniform size indicates a well-defined composition of protein and polymer, which is essential for applications that request a precise control of the dosage of enzyme activity. Copyright © 2011. Published by Elsevier Ltd.

  10. Efficient inverted polymer solar cells based on conjugated polyelectrolyte and zinc oxide modified ITO electrode

    Energy Technology Data Exchange (ETDEWEB)

    Yuan, Tao; Zhu, Xiaoguang; Tu, Guoli, E-mail: tgl@hust.edu.cn [Wuhan National Laboratory for Optoelectronics, Huazhong University of Science and Technology, Wuhan 430074 (China); Zhou, Lingyu [State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian National Laboratory of Clean Energy, Dalian 116023 (China); Zhang, Jian, E-mail: jianzhang@guet.edu.cn [Department of Material Science and Engineering, Guangxi Key Laboratory of Information Materials, Guilin University of Electronic Technology, Guilin 541004 (China)

    2015-02-23

    Efficient inverted polymer solar cells (PSCs) were constructed by utilizing a conjugated polyelectrolyte PF{sub EO}SO{sub 3}Na and zinc oxide to modify the indium tin oxide (ITO) electrode. The ITO electrode modified by PF{sub EO}SO{sub 3}Na and zinc oxide possesses high transparency, increased electron mobility, smoothened surface, and lower work function. PTB7:PC{sub 71}BM inverted PSCs containing the modified ITO electrode achieved a high power conversion efficiency (PCE) of 8.49%, exceeding that of the control device containing a ZnO modified ITO electrode (7.48%). Especially, PCE-10:PC{sub 71}BM inverted polymer solar cells achieved a high PCE up to 9.4%. These results demonstrate a useful approach to improve the performance of inverted polymer solar cells.

  11. Efficient inverted polymer solar cells based on conjugated polyelectrolyte and zinc oxide modified ITO electrode

    Science.gov (United States)

    Yuan, Tao; Zhu, Xiaoguang; Zhou, Lingyu; Zhang, Jian; Tu, Guoli

    2015-02-01

    Efficient inverted polymer solar cells (PSCs) were constructed by utilizing a conjugated polyelectrolyte PFEOSO3Na and zinc oxide to modify the indium tin oxide (ITO) electrode. The ITO electrode modified by PFEOSO3Na and zinc oxide possesses high transparency, increased electron mobility, smoothened surface, and lower work function. PTB7:PC71BM inverted PSCs containing the modified ITO electrode achieved a high power conversion efficiency (PCE) of 8.49%, exceeding that of the control device containing a ZnO modified ITO electrode (7.48%). Especially, PCE-10:PC71BM inverted polymer solar cells achieved a high PCE up to 9.4%. These results demonstrate a useful approach to improve the performance of inverted polymer solar cells.

  12. Aromatic Schiff Bases Multiply Substituted with Terminal Ethynyl Groups: Potential Building Blocks for Conjugated Polymers and Oligomers

    Czech Academy of Sciences Publication Activity Database

    Stahlová, S.; Sedláček, J.; Svoboda, J.; Polášek, Miroslav; Zednik, J.

    2015-01-01

    Roč. 68, č. 8 (2015), s. 1237-1248 ISSN 0004-9425 R&D Projects: GA ČR GAP108/12/1143 Grant - others:GA MŠk(CZ) LM2010005 Institutional support: RVO:61388955 Keywords : Aromatic compounds * Aromatic polymers * Conjugated polymers Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 1.427, year: 2015

  13. Extraordinary Capability for Water Treatment Achieved by a Perfluorous Conjugated Microporous Polymer

    Science.gov (United States)

    Yang, Rui-Xia; Wang, Ting-Ting; Deng, Wei-Qiao

    2015-01-01

    Oils, organic solvents, dyes, and heavy metal ions are primary pollutants in water resources. Currently, no sorbent material can effectively remove these types of pollutants simultaneously. Here we report a perfluorous conjugated microporous polymer with superhydrophobicity and a large surface area, which exhibits outstanding adsorption capacities, kinetics, and recyclability for a wide range of organic solvents, oils, dyes, and heavy metal ions. The adsorption capacities of this polymer, 1376.7 mg g−1 for Congo red, 808.2 mg g−1 for Pb(II) and 303.2 mg g−1 for As(V), are higher than the adsorption capacities of any previously described porous materials. Our theoretical calculation reveals that the superior properties of this polymer are due to fluorination and triple bonds within the polymer. A benchmark experiment indicates that this polymer can efficiently remove these pollutants simultaneously. Application of this polymer may lead to the development of next-generation reusable and portable water purification appliances. PMID:25974738

  14. Bioconcentration of Water Soluble Fraction (WSF) of crude oil in ...

    African Journals Online (AJOL)

    Bioconcentration of water soluble fraction of Australian crude oil in 50 fingerlings of Oreochromis niloticus was conducted under laboratory conditions for 28 days. An initial acute toxicity test was carried out using different concentrations (25ml/L, 50ml/L, 75ml/L, 100ml/L and a control) of the water soluble fraction (WSF) of ...

  15. 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.

  16. Novel Design Strategies for Platinum-Containing Conjugated Polymers and Small Molecules for Organic Solar Cells

    Science.gov (United States)

    He, Wenhan

    Current state-of-the-art organic solar cells (OSCs) adopt the strategy of using conjugated polymers or small molecules as donors and fullerene derivatives as acceptors in their active layers. Regarding to the donors of interest, the conjugated polymers and small molecules coupled with heavy metals have been less explored compared to their counterparts. Among various transition metal complexes applied, Pt(II) complexes are unique because of their intrinsic square planar geometries and ability to serve as building blocks for conjugated systems. Furthermore, the heavy metal Pt facilitates the formation of triplet excitons with longer life times through spin-orbital coupling which are of benefit for the OSCs application. However, in order to obtain low bandgap polymers, people are intended to use chromophores with long conjugated length, nevertheless such design will inevitably dilute the spin-orbital coupling effect and finally influence the formation of triplet excitons. Furthermore, the majority of Pt-containing conjugated systems reported so far shared a common feature-- they all possessed "dumbbell" shaped structures and were amorphous, leading to poor device performance. In addition, there were few examples reporting the capture of the triplet excitons by the fullerene acceptors in the OSCs since there is a mismatch between the triplet energy state (T1) of the Pt-containing compounds and the LUMO level of fullerene acceptors. As a result, these three intrinsic problems will impede the further development of such a field. In order to solve these problems, I originally designed and synthesized three novel compounds with unique proprieties named as Bodipy-Pt, Pt-SM and C60+SDS-. Specifically, Bodipy has the advantages of compact size, easy to synthesis and high fluorescence quantum yield which can effectively solve the problem of long conjugated length. While in terms of second problem, the new Pt-SM possessed a "roller-wheel" structural design with increased

  17. 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.

  18. Silica-shell cross-linked micelles encapsulating fluorescent conjugated polymers for targeted cellular imaging.

    Science.gov (United States)

    Tan, Happy; Zhang, Yu; Wang, Miao; Zhang, Zhongxing; Zhang, Xinhai; Yong, Anna Marie; Wong, Siew Yee; Chang, Alex Yuang-chi; Chen, Zhi-Kuan; Li, Xu; Choolani, Mahesh; Wang, John

    2012-01-01

    A bioinspired silification approach was successfully used to encapsulate fluorescent conjugated polymers inside silica-shell cross-linked polymeric micelles (CP-SSCL) in the highly benign synthesis environment of room temperature and near-neutral aqueous environment. Four different conjugated polymers were employed to demonstrate the versatility of the bioinspired silification, resulting in the formation of CP-SSCL with different emission wavelengths across the visible spectrum. The CP-SSCL are characterized by a large absorption coefficient and high quantum yield, indicating that they exhibit the required high fluorescence brightness for cellular imaging application. In addition, the CP-SSCL also exhibit a high colloidal stability and low cytotoxicity. The in vitro studies of using MDA-MB-231 breast cancer cells show that the CP-SSCL are successfully uptaken by the cancer cells and located at the cytoplasm of the cells. Furthermore, by conjugating folic acid on their surfaces, the uptake of CP-SSCL by MDA-MB-231 cells was enhanced significantly, suggesting their great potential for targeted imaging and early detection of cancer cells. Copyright © 2011 Elsevier Ltd. All rights reserved.

  19. Capture and Reversible Storage of Volatile Iodine by Novel Conjugated Microporous Polymers Containing Thiophene Units.

    Science.gov (United States)

    Qian, Xin; Zhu, Zhao-Qi; Sun, Han-Xue; Ren, Feng; Mu, Peng; Liang, Weidong; Chen, Lihua; Li, An

    2016-08-17

    Conjugated microporous polymers having thiophene building blocks (SCMPs), which originated from ethynylbenzene monomers with 2,3,5-tribromothiophene, were designedly synthesized through Pd(0)/CuI catalyzed Sonogashira-Hagihara cross-coupling polymerization. The morphologies, structure and physicochemical properties of the as-synthesized products were characterized through scanning electron microscope (SEM), thermogravimeter analysis (TGA), (13)C CP/MAS solid state NMR and Fourier transform infrared spectroscope (FTIR) spectra. Nitrogen sorption-desorption analysis shows that the as-synthesized SCMPs possesses a high specific surface area of 855 m(2) g(-1). Because of their abundant porosity, π-conjugated network structure, as well as electron-rich thiophene building units, the SCMPs show better adsorption ability for iodine and a high uptake value of 222 wt % was obtained, which can compete with those nanoporous materials such as silver-containing zeolite, metal-organic frameworks (MOFs) and conjugated microporous polymers (CMPs), etc. Our study might provide a new possibility for the design and synthesis of functional CMPs containing electron-rich building units for effective capture and reversible storage of volatile iodine to address environmental issues.

  20. Development of PDT/PET Theranostics: Synthesis and Biological Evaluation of an (18)F-Radiolabeled Water-Soluble Porphyrin.

    Science.gov (United States)

    Entract, Guy M; Bryden, Francesca; Domarkas, Juozas; Savoie, Huguette; Allott, Louis; Archibald, Stephen J; Cawthorne, Chris; Boyle, Ross W

    2015-12-07

    Synthesis of the first water-soluble porphyrin radiolabeled with fluorine-18 is described: a new molecular theranostic agent which integrates the therapeutic selectivity of photodynamic therapy (PDT) with the imaging efficacy of positron emission tomography (PET). Generation of the theranostic was carried out through the conjugation of a cationic water-soluble porphyrin bearing an azide functionality to a fluorine-18 radiolabeled prosthetic bearing an alkyne functionality through click conjugation, with excellent yields obtained in both cold and hot synthesis. Biological evaluation of the synthesized structures shows the first example of an (18)F-radiolabeled porphyrin retaining photocytotoxicity following radiolabeling and demonstrable conjugate uptake and potential application as a radiotracer in vivo. The promising results gained from biological evaluation demonstrate the potential of this structure as a clinically relevant theranostic agent, offering exciting possibilities for the simultaneous imaging and photodynamic treatment of tumors.

  1. 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.

  2. 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.

  3. 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.

  4. 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.

  5. Multiplexed detection of protein cancer markers on Au/Ag-barcoded nanorods using fluorescent-conjugated polymers.

    Science.gov (United States)

    Zheng, Weiming; He, Lin

    2010-07-01

    Integration of fluorescent-conjugated polymers as detection moiety with metallic striped nanorods for multiplexed detection of clinically important cancer marker proteins in an immunoassay format was demonstrated in this report. Specifically, cationic conjugated polymers were introduced to protein complexes through electrostatic binding to negatively charged double-stranded DNA, which was tagged on detection antibodies prior to antigen recognition. The intense fluorescence emission of conjugated polymers resulted in highly sensitive detection of cancer marker proteins wherein an undiluted bovine serum sample as low as approximately 25 target molecules captured on each particle was detectable. Meanwhile, the use of polymer molecules as the detection probe did not obscure the optical pattern of underlying nanorods, i.e., the encoding capability of barcoded nanorods was preserved, which allowed simultaneous detection of three cancer marker proteins with good specificity.

  6. 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

    effects of stretching the conjugated polymer of MEH-PPV (Mw = 55kg/mole) on the photoluminescence behavior was further studied in the experiment of...in Opto- and Electro-Excitated Conjugated Polymers for High- Efficiency Optoelectronic Devices 5a. CONTRACT NUMBER FA2386-12-1-4064 5b. GRANT...The role of mechanical stresses in the optoelectronic behavior and exciton formation of conjugated polymers was explored in order to understand and to

  7. Medium Bandgap Conjugated Polymer for High Performance Polymer Solar Cells Exceeding 9% Power Conversion Efficiency.

    Science.gov (United States)

    Jung, Jae Woong; Liu, Feng; Russell, Thomas P; Jo, Won Ho

    2015-12-02

    Two medium-bandgap polymers composed of benzo[1,2-b:4,5-b']dithiohpene and 2,1,3-benzothiadiazole with 6-octyl-thieno[3,2-b]thiophene as a π-bridge unit are synthesized and their photovoltaic properties are analyzed. The two polymers have deep highest occupied molecular orbital energy levels, high crystallinity, optimal bulk-heterojunction morphology, and efficient charge transport, resulting in a power conversion efficiency of as high as 9.44% for a single-junction polymer solar-cell device. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. Universality in unintentional laser resonators in π-conjugated polymer films

    Science.gov (United States)

    Polson, Randall C.; Raikh, Mikhail E.; Vardeny, Z. Valy

    When films of π-conjugated polymers are optically excited above a certain threshold intensity, then the emission spectrum acquires a multimode finely structured shape, which depends on the position of the excitation spot. We demonstrate that the power Fourier transform (PFT) of the emission spectrum exhibits a certain peak-like structure, which also depends on the excitation spot. Our intriguing observation is that averaging the individual PFTs does not lead to a structureless curve, but rather yields a series of distinct transform peaks. This suggests universality, namely that the underlying random resonators that are responsible for the laser emission from the π-conjugated polymer film are almost identical. We argue that the reason for such an universality is the large size of a typical resonator, which we determined from the PFT, as compared to the emission wavelength, λ. This fact is, in turn, a consequence of the large light mean free path, l ∗≃10λ in the polymer film. This contrasts previous observations of random lasing in powders, where l ∗˜λ . We develop a simple theory that explains the presence of peaks in the average PFT and predicts their shape. The results of the theory agree quantitatively with the data. To cite this article: R.C. Polson et al., C. R. Physique 3 (2002) 509-521.

  9. Conjugated polymers as functional hole selective layers in efficient metal halide perovskite solar cells

    Directory of Open Access Journals (Sweden)

    Silvia Colodrero

    2017-08-01

    Full Text Available Interface engineering is still an open question to be solved in the emerging field of metal halide perovskite solar cells. Although impressive advances have been already made in controlling the composition and the quality of the active layer, stability issues of complete devices are limiting yet the forefront of a future next generation of printable photovoltaics. At this point, the choice of proper charge selective layers is essential to yield perovskite solar cells with an optimal compromise between efficiency and stability. Even though diverse n-type materials displaying outstanding properties have been recently proposed, the record performances are yet limited to the use of p-type small molecule compounds with low hole mobility in their pristine form. In here, conjugated polymers widely used in the field of polymer solar cells are integrated in perovskite devices to behave as the hole selective layers. Apart from offering suitable hole mobility and energy matching with the valence band of the perovskite material to enable efficient charge extraction, their behaviour as potential functional barrier to protect the underlying perovskite film in standard n-i-p architectures is also discussed. Future work focused on developing novel alternatives based on more stable and efficient conjugated polymers might pave the way for the large scale production of perovskite solar cells.

  10. 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.

  11. Preparation and photo-catalytic behavior of conjugated polymers based on paper-making wastewater.

    Science.gov (United States)

    Feng, Libang; Qiang, Xiaohu; Shi, Xueting

    2009-08-01

    Based on alkaline paper-making wastewater, a polymer catalyst (FQ) was prepared and characterized by FTIR, ESR and element analysis techniques. The results show that the catalyst has conjugated structure and the conjugate degree increases after heat treatment. The catalyst has quite high photo-catalytic activity, which was verified by the fact that the simulated dyeing wastewater containing methylene blue (MB) or acridine orange (AO) can be degraded completely in 20 minutes under natural light using FQ as the photo-catalyst. Therefore, the synthetic dyeing wastewater can be disposed of using the materials coming from paper-making wastewater. It is a very promising method to treat one kind of wastewater with the materials from another kind of wastewater.

  12. Donor-acceptor conjugated polymers based on multifused ladder-type arenes for organic solar cells.

    Science.gov (United States)

    Wu, Jhong-Sian; Cheng, Sheng-Wen; Cheng, Yen-Ju; Hsu, Chain-Shu

    2015-03-07

    Harvesting solar energy from sunlight to generate electricity is considered as one of the most important technologies to address the future sustainability of humans. Polymer solar cells (PSCs) have attracted tremendous interest and attention over the past two decades due to their potential advantage to be fabricated onto large area and light-weight flexible substrates by solution processing at a lower cost. PSCs based on the concept of bulk heterojunction (BHJ) configuration where an active layer comprises a composite of a p-type (donor) and an n-type (acceptor) material represents the most useful strategy to maximize the internal donor-acceptor interfacial area allowing for efficient charge separation. Fullerene derivatives such as [6,6]-phenyl-C61 or 71-butyric acid methyl ester (PCBM) are the ideal n-type materials ubiquitously used for BHJ solar cells. The major effort to develop photoactive materials is numerously focused on the p-type conjugated polymers which are generally synthesized by polymerization of electron-rich donor and electron-deficient acceptor monomers. Compared to the development of electron-deficient comonomers (acceptor segments), the development of electron-rich donor materials is considerably flourishing. Forced planarization by covalently fastening adjacent aromatic and heteroaromatic subunits leads to the formation of ladder-type conjugated structures which are capable of elongating effective conjugation, reducing the optical bandgap, promoting intermolecular π-π interactions and enhancing intrinsic charge mobility. In this review, we will summarize the recent progress on the development of various well-defined new ladder-type conjugated materials. These materials serve as the superb donor monomers to prepare a range of donor-acceptor semi-ladder copolymers with sufficient solution-processability for solar cell applications.

  13. Design, synthesis, fabrication and in vitro evalution of mucoadhesive 5-amino-2-mercaptobenzimidazole chitosan as low water soluble drug carriers.

    Science.gov (United States)

    Kongsong, Mullika; Songsurang, Kultida; Sangvanich, Polkit; Siralertmukul, Krisana; Muangsin, Nongnuj

    2014-11-01

    Mucoadhesive thiolated chitosan suitable as a carrier for low water soluble drugs was designed and synthesized by conjugating 5-amino-2-mercaptobenzimidazole (MBI) using methylacrylate (MA) as the linking agent. A 14.4% degree of substitution of MA, as determined by (1)H NMR analysis, and 11.86±0.01μmol thiol groups/g of polymer, as determined by Ellman's method, was obtained. The MBI-MA-chitosan had an 11-fold stronger mucoadhesive property compared to unmodified chitosan at pH 1.2, as determined by the periodic acid: Schiff colorimetric method. Chitosan, MA-chitosan and MBI-MA-chitosan were fabricated as well-formed microspheres using electrospray ionization, including an entrapment efficiency of simvastatin (SV) of over 80% for the MBI-MA-chitosan. The mucoadhesiveness of the SV-loaded MBI-MA-CS microspheres was still higher than that for SV-loaded chitosan at pH 1.2 and 6.4. The SV-loaded MBI-MA-CS microspheres revealed a reduced burst effect and an increased release rate (more than fivefold higher than pure SV) of SV over 12h. Copyright © 2014 Elsevier B.V. All rights reserved.

  14. Effect of conjugation on phase transitions in thermoresponsive polymers: an atomistic and coarse-grained simulation study.

    Science.gov (United States)

    Condon, Joshua E; Martin, Tyler B; Jayaraman, Arthi

    2017-04-19

    Using atomistic and coarse-grained molecular dynamics (MD) simulations, we explain the shifts in lower critical solution temperature (LCST)-like phase transitions exhibited by elastin-like peptides (ELPs) upon conjugation to other macromolecules (e.g. collagen-like peptides or CLPs). First, using atomistic simulations, we study ELP oligomers with the sequence (VPGFG)6 in explicit water, and characterize the LCST-like transition temperature as one at which the ELP oligomers undergo a change in "hydration state". In agreement with past experimental observations of Luo and Kiick, upon anchoring ELP oligomers to a point to mimic ELP oligomers conjugated to another macromolecule, there is an apparent slight shift in the transition temperature to lower values compared to free (unconjugated) ELP oligomers. However, these atomistic simulations are limited to small systems of short ELPs, and as such do not capture the multiple chain aggregation/phase separation observed in experiments of ELPs. Therefore, we utilize phenomenological coarse-grained (CG) MD simulations to probe how conjugating a block of generic-LCST polymer to another rigid unresponsive macromolecular block impacts the transition temperatures at concentrations and length scales larger than atomistic simulations. We find that when multiple LCST polymer chains are conjugated to a rigid unresponsive polymer block, the increased local crowding of the LCST polymers shifts the transition marked by onset of chain aggregation to smaller effective polymer-polymer attraction energies compared to the free LCST polymer chains. The driving force needed for aggregation is reduced in the conjugates compared to free LCST polymer due to reduction in the loss of polymer configurational entropy upon aggregation.

  15. Aggregation control in natural brush-printed conjugated polymer films and implications for enhancing charge transport.

    Science.gov (United States)

    Wang, Gang; Huang, Wei; Eastham, Nicholas D; Fabiano, Simone; Manley, Eric F; Zeng, Li; Wang, Binghao; Zhang, Xinan; Chen, Zhihua; Li, Ran; Chang, Robert P H; Chen, Lin X; Bedzyk, Michael J; Melkonyan, Ferdinand S; Facchetti, Antonio; Marks, Tobin J

    2017-11-21

    Shear-printing is a promising processing technique in organic electronics for microstructure/charge transport modification and large-area film fabrication. Nevertheless, the mechanism by which shear-printing can enhance charge transport is not well-understood. In this study, a printing method using natural brushes is adopted as an informative tool to realize direct aggregation control of conjugated polymers and to investigate the interplay between printing parameters, macromolecule backbone alignment and aggregation, and charge transport anisotropy in a conjugated polymer series differing in architecture and electronic structure. This series includes (i) semicrystalline hole-transporting P3HT, (ii) semicrystalline electron-transporting N2200, (iii) low-crystallinity hole-transporting PBDTT-FTTE, and (iv) low-crystallinity conducting PEDOT:PSS. The (semi-)conducting films are characterized by a battery of morphology and microstructure analysis techniques and by charge transport measurements. We report that remarkably enhanced mobilities/conductivities, as high as 5.7×/3.9×, are achieved by controlled growth of nanofibril aggregates and by backbone alignment, with the adjusted R2 (R2adj) correlation between aggregation and charge transport as high as 95%. However, while shear-induced aggregation is important for enhancing charge transport, backbone alignment alone does not guarantee charge transport anisotropy. The correlations between efficient charge transport and aggregation are clearly shown, while mobility and degree of orientation are not always well-correlated. These observations provide insights into macroscopic charge transport mechanisms in conjugated polymers and suggest guidelines for optimization.

  16. 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.

  17. Preparation and evaluation of high dispersion stable nanocrystal formulation of poorly water-soluble compounds by using povacoat.

    Science.gov (United States)

    Yuminoki, Kayo; Seko, Fuko; Horii, Shota; Takeuchi, Haruka; Teramoto, Katsuya; Nakada, Yuichiro; Hashimoto, Naofumi

    2014-11-01

    In this study, we reported the application of Povacoat®, a hydrophilic polyvinylalcohol copolymer, as a dispersion stabilizer of nanoparticles of poorly water-soluble compounds. In addition, the influence of aggregation of the nanoparticles on their solubility and oral absorption was studied. Griseofulvin (GF) was used as a model compound with poor water solubility and was milled to nanoparticles by wet bead milling. The dispersion stability of GF milled with Povacoat® or the generally used polymers (polyvinylalcohol, hydroxypropylcellulose SSL, and polyvinylpyrrolidone K30) was compared. Milled GF suspended in Povacoat® aqueous solution with D-mannitol, added to improve the disintegration rate of freeze-dried GF, exhibited high dispersion stability without aggregation (D90 = ca. 0.220 μm), whereas milled GF suspended in aqueous solutions of the other polymers aggregated (D90 > 5 μm). Milled GF with Povacoat® showed improved aqueous solubility and bioavailability compared with the other polymers. The aggregation of nanoparticles had significant impact on the solubility and bioavailability of GF. Povacoat® also prevented the aggregation of the various milled poorly water-soluble compounds (hydrochlorothiazide and tolbutamide, etc.) more effectively than the other polymers. These results showed that Povacoat® could have wide applicability to the development of nanoformulations of poorly water-soluble compounds. © 2014 Wiley Periodicals, Inc. and the American Pharmacists Association.

  18. Water-soluble dietary fibers and cardiovascular disease.

    Science.gov (United States)

    Theuwissen, Elke; Mensink, Ronald P

    2008-05-23

    One well-established way to reduce the risk of developing cardiovascular disease (CVD) is to lower serum LDL cholesterol levels by reducing saturated fat intake. However, the importance of other dietary approaches, such as increasing the intake of water-soluble dietary fibers is increasingly recognized. Well-controlled intervention studies have now shown that four major water-soluble fiber types-beta-glucan, psyllium, pectin and guar gum-effectively lower serum LDL cholesterol concentrations, without affecting HDL cholesterol or triacylglycerol concentrations. It is estimated that for each additional gram of water-soluble fiber in the diet serum total and LDL cholesterol concentrations decrease by -0.028 mmol/L and -0.029 mmol/L, respectively. Despite large differences in molecular structure, no major differences existed between the different types of water-soluble fiber, suggesting a common underlying mechanism. In this respect, it is most likely that water-soluble fibers lower the (re)absorption of in particular bile acids. As a result hepatic conversion of cholesterol into bile acids increases, which will ultimately lead to increased LDL uptake by the liver. Additionally, epidemiological studies suggest that a diet high in water-soluble fiber is inversely associated with the risk of CVD. These findings underlie current dietary recommendations to increase water-soluble fiber intake.

  19. 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...

  20. Novel fluorescent biosensor for α-glucosidase inhibitor screening based on cationic conjugated polymers.

    Science.gov (United States)

    Cao, Ali; Tang, Yanli; Liu, Yue

    2012-08-01

    A new fluorescent biosensor has been designed to screen α-glucosidase inhibitors (AGIs) sensitively by utilizing signal amplification effect of conjugated polymers. The fluorescence of cationic poly(fluorenylene phenylene) (PFP) was quenched in the presence of para-nitrophenyl-α-d-glucopyranoside and α-glucosidase, and turned on upon addition of AGIs. Thus, a new method was developed for AGIs screening based on the fluorescence turn-off/turn-on. The IC(50) values obtained for inhibitors were compared with that reported using absorption spectroscopy. All results present the new method is more sensitive and promising in screening AGIs and inhibitors of other enzymes whose hydrolysis product is 4-nitrophenol.

  1. Nanocomposites obtained by embedding of conjugated polymers in porous silicon and silica

    Energy Technology Data Exchange (ETDEWEB)

    Errien, N.; Vellutini, L.; Froyer, G.; Louarn, G. [Institut des Materiaux Jean Rouxel, LPC, 2 rue de la houssiniere, BP 3229, 44322 Nantes Cedex 3 (France); Simos, C.; Skarka, V. [Laboratoire POMA, Universite d' Angers, 2 bd Lavoisier, 49045 Angers Cedex 01 (France); Haesaert, S.; Joubert, P. [Laboratoire d' Optronique de Lannion, Rue E. Branly, BP 150, 22302 Lannion Cedex (France)

    2005-06-01

    Porous silicon and porous silica matrices are filled up by conjugated polymers in order to obtain nanocomposite with enhanced third order optical nonlinearity. The active component is either PDA-TS thermally polymerized in situ or PT12 electropolymerized in porous silicon. The first measurements of the nonlinear properties of these nanocomposites give evidence of a significant increase of the nonlinear refractive index with respect to the standard optical materials. (copyright 2005 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim) (orig.)

  2. Optical Properties and Sequence Information of Tin-Centered Conjugated Microporous Polymers.

    Science.gov (United States)

    Uptmoor, Andrea C; Ilyas, Ruben; Elbert, Sven M; Wacker, Irene; Schröder, Rasmus R; Mastalerz, Michael; Freudenberg, Jan; Bunz, Uwe H F

    2018-02-01

    We synthesized conjugated microporous polymers (CMPs) based on tetrakis(4-ethynylphenyl)stannane and diiodobenzene as tectons, using Sonogashira couplings under different conditions. Through variation of the reaction conditions (catalysts, bases and solvents), appearance, surface area and emission properties of the formed CMPs were significantly altered. Wet-chemical, acid-mediated digestion and analysis of the resulting struts of these otherwise insoluble networks give insight into the molecular setup. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. A Highly Crystalline Wide-Band-Gap Conjugated Polymer toward High-Performance As-Cast Nonfullerene Polymer Solar Cells.

    Science.gov (United States)

    Jiang, Haiying; Wang, Zhen; Zhang, Lianjie; Zhong, Anxing; Liu, Xuncheng; Pan, Feilong; Cai, Wanzhu; Inganäs, Olle; Liu, Yi; Chen, Junwu; Cao, Yong

    2017-10-18

    A new wide-band-gap conjugated polymer PBODT was successfully synthesized that showed high crystallinity and was utilized as the active material in nonfullerene bulk-heterojunction polymer solar cells (PSCs). The photovoltaic devices based on the as-cast blend films of PBODT with ITIC and IDIC acceptors showed notable power conversion efficiencies (PCEs) of 7.06% and 9.09%, with high open-circuit voltages of 1.00 and 0.93 V that correspond to low energy losses of 0.59 and 0.69 eV, respectively. In the case of PBODT:ITIC, lower exciton quenching efficiency and monomolecular recombination are found for devices with small driving force. On the other hand, the relatively higher driving force and suppressed monomolecular recombination for PBODT:IDIC devices are identified to be the reason for their higher short-circuit current density (Jsc) and higher PCEs. In addition, when processed with the nonchlorinated solvent 1,2,4-trimethylbenzene, a good PCE of 8.19% was still achieved for the IDIC-based device. Our work shows that such wide-band-gap polymers have great potential for the environmentally friendly fabrication of highly efficient PSCs.

  4. 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.

  5. 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.

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

    Science.gov (United States)

    Jiwuer, Jilili; Abdurahman, Ayjamal; Gülseren, Oğuz; Schwingenschlögl, Udo

    2015-03-01

    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 (GGA) a non-binding state, whereas the local density approximation (LDA) predicts reasonable binding energies. The results coincide after inclusion of van der Waals (vdW) 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. Research reported in this publication was supported by the King Abdullah University of Science and Technology (KAUST).

  7. 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.

  8. Design of Chitosan and Its Water Soluble Derivatives-Based Drug Carriers with Polyelectrolyte Complexes

    Directory of Open Access Journals (Sweden)

    Qing-Xi Wu

    2014-12-01

    Full Text Available Chitosan, the cationic polysaccharide derived from the natural polysaccharide chitin, has been studied as a biomaterial for more than two decades. As a polycationic polymer with favorable properties, it has been widely used to form polyelectrolyte complexes with polyanions for various applications in drug delivery fields. In recent years, a growing number of studies have been focused on the preparation of polyelectrolyte complexes based on chitosan and its water soluble derivatives. They have been considered well-suited as biomaterials for a number of vital drug carriers with targeted/controlled release profiles, e.g., films, capsules, microcapsules. In this work, an overview highlights not only the favorable properties of chitosan and its water soluble derivatives but also the good performance of the polyelectrolyte complexes produced based on chitosan. Their various types of applications as drug carriers are reviewed in detail.

  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. Fabrication of a conjugated microporous polymer membrane and its application for membrane catalysis.

    Science.gov (United States)

    Lee, Jieun; Kim, Jong Gil; Chang, Ji Young

    2017-10-19

    A flexible and free standing conjugated microporous polymer (CMP) membrane was prepared using a polyvinylpyrrolidone (PVP) electrospun membrane as a template. The PVP nanofibers of the template membrane were coated with a thin layer of the CMP through the in situ Sonogashira-Hagihara coupling reaction of 1,3,5-triethynylbenzene and 1,4-diiodobenzene. The PVP nanofibers were removed by the solvent extraction to produce the CMP membrane, which retained the entangled fibrous structure of the template membrane. Each fiber showed a hollow tubular structure having a CMP wall with a thickness of tens of nanometers. The microporous polymer membrane exhibited a high BET surface area with hierarchical porosity and good permeability. As a catalytic CMP membrane, the Ag nanoparticle-immobilized microporous polymer membrane was fabricated using an electrospun PVP@Ag membrane as a template. After being coated with the CMP, the PVP nanofibers were removed by the solvent extraction, but the Ag nanoparticles were trapped in the microporous polymer shell. The catalytic CMP membrane was successfully used for the catalytic reduction reaction of 4-nitrophenol. The hollow tubular structure and hierarchical porosity of the membrane allowed for the reactants to easily penetrate into the CMP wall and to contact the Ag nanoparticles, resulting in the high catalytic activity.

  11. Protonation process of conjugated polyelectrolytes on enhanced power conversion efficiency in the inverted polymer solar cells

    Science.gov (United States)

    Yi, Chao; Hu, Rong; Ren, He; Hu, Xiaowen; Wang, Shu; Gong, Xiong; Cao, Yong

    2014-01-01

    In this study, two conjugated polyelectrolytes, polythiophene derivative (PTP) and poly[(9,9-bis [6‧-N, N, N-trimethylammonium] hexyl)-fluorenylene-phenylene] dibromide (PFP), are utilized to modify the surface properties of ZnO electron extraction layer (EEL) in the inverted polymer solar cells (PSCs). Both higher short-circuit current densities and larger open-circuit voltages were observed from the inverted PSCs with ZnO/PFP or ZnO/PTP as compared with those only with ZnO EEL. The protonation process for PTP and PFP in solution is distinguished. Overall, more than 40% enhanced power conversion efficiency (PCE) from the inverted PSCs with ZnO/PFP, in which the PFP could be fully ionized in deionized water, and more than 30% enhanced PCE from the inverted PSCs with ZnO/PTP, as the case that the PTP could not be fully ionized in deionized water, as compared with the inverted PSCs with ZnO EEL were observed, respectively. These results demonstrate that the conjugated polyelectrolytes play an important role in enhancement of device performance of inverted PSCs and that the protonation process of the conjugated polyelectrolytes is critical to the modification for EEL in PSCs.

  12. 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.

  13. Donor-acceptor conjugated polymers used as electron acceptors in bulk heterojunction photovoltaics

    Science.gov (United States)

    Bailey, Christopher; Taylor, Barney; Mei, Jianguo; Reynolds, John; Henderson, John; Leever, Benjamin; Durstock, Michael

    2011-03-01

    Synthetic control over the Highest Occupied Molecular Orbital (HOMO) and Lowest Unoccupied Molecular Orbital (LUMO) has been of significant importance in organic photovoltaics due to the nature of charge separation in donor/acceptor blends. One technique for obtaining tunability of the HOMO and LUMO levels with polymer synthesis is to combine electron donating and electron accepting moieties separated by a conjugated linkage unit. This technique has been utilized to produce highly efficient devices reaching power conversion efficiencies above 8% in polymer/fullerene blends. In this work, we report the characterization of poly(2,7-divinylene fluorene-co-benzothiadiazole) (F10DVBT), and performs best as an electron acceptor when mixed with poly(3-hexylthiophene) (P3HT) with an open circuit voltage of 1.2V. A combination of morphological and photo-physical studies highlights interesting properties of this material and its interactions with P3HT. The donor-acceptor conjugated structure of F10DVBT appears to strongly affect the photocurrent of these devices, and may result from the interactions between intramolecular and intermolecular charge transfer processes.

  14. Photocurrent generation in carbon nitride and carbon nitride/conjugated polymer composites.

    Science.gov (United States)

    Byers, Joshua C; Billon, Florence; Debiemme-Chouvy, Catherine; Deslouis, Claude; Pailleret, Alain; Semenikhin, Oleg A

    2012-09-26

    The semiconductor and photovoltaic properties of carbon nitride (CNx) thin films prepared using a reactive magnetron cathodic sputtering technique were investigated both individually and as composites with an organic conjugated polymer, poly(2,2'-bithiophene) (PBT). The CNx films showed an increasing thickness as the deposition power and/or nitrogen content in the gas mixture increase. At low nitrogen content and low deposition power (25-50 W), the film structure was dominated by the abundance of the graphitic sp(2) regions, whereas at higher nitrogen contents and magnetron power CNx films started to demonstrate semiconductor properties, as evidenced by the occurrence of photoconductivity and the development of a space charge region. However, CNx films alone did not show any reproducible photovoltaic properties. The situation changed, however, when CNx was deposited onto conjugated PBT substrates. In this configuration, CNx was found to function as an acceptor material improving the photocurrent generation both in solution and in solid state photovoltaic devices, with the external quantum efficiencies reaching 1% at high nitrogen contents. The occurrence of the donor-acceptor charge transfer was further evidenced by suppression of the n-doping of the PBT polymer by CNx. Nanoscale atomic force microscopy (AFM) and current-sensing AFM data suggested that CNx may form a bulk heterojunction with PBT.

  15. Silica nanocapsules of fluorescent conjugated polymers and superparamagnetic nanocrystals for dual-mode cellular imaging.

    Science.gov (United States)

    Tan, Happy; Wang, Miao; Yang, Chang-Tong; Pant, Shilpa; Bhakoo, Kishore Kumar; Wong, Siew Yee; Chen, Zhi-Kuan; Li, Xu; Wang, John

    2011-06-06

    We describe here a facile and benign synthetic strategy to integrate the fluorescent behavior of conjugated polymers and superparamagnetic properties of iron oxide nanocrystals into silica nanocapsules, forming a new type of bifunctional magnetic fluorescent silica nanocapsule (BMFSN). The resultant BMFSNs are uniform, colloidally stable in aqueous medium, and exhibit the desired dual functionality of fluorescence and superparamagnetism in a single entity. Four conjugated polymers with different emissions were used to demonstrate the versatility of employing this class of fluorescent materials for the preparation of BMFSNs. The applicability of BMFSNs in cellular imaging was studied by incubating them with human liver cancer cells, the result of which demonstrated that the cells could be visualized by dual-mode fluorescence and magnetic resonance imaging. Furthermore, the superparamagnetic behavior of the BMFSNs was exploited for in vitro magnetic-guided delivery of the nanocapsules into the cancer cells, thereby highlighting their potential for targeting biomedical applications. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. Fluorene-Based Conjugated Microporous Polymers: Preparation and Chemical Sensing Application.

    Science.gov (United States)

    Zhang, Qiujing; Yu, Sen; Wang, Qian; Xiao, Qin; Yue, Yong; Ren, Shijie

    2017-12-01

    Conjugated microporous polymers (CMPs) with strong fluorescence are great candidates for optoelectronic applications such as photocatalysis and chemical sensing. A series of novel fluorene-based conjugated microporous polymers (FCMPs) with different electronic structures are prepared by Yamamoto coupling reactions using rationally designed monomers. The FCMPs show a high degree of microporosity, decent specific surface areas, and variable fluorescence. FCMP3, which possesses a triazine knot in the network, exhibits the highest specific surface area of 489 m2 g-1 , the largest pore volume of 0.30 cm3 g-1 , and the highest solid-state photoluminescence quantum yield of 11.46%. Chemical sensing performance of FCMPs is studied using a range of nitroaromatic compounds as the analytes. Among the FCMPs, FCMP3 exhibits the highest Stern-Volmer constants of 2541, 4708, and 5241 m-1 for the detection of nitrobenzene, 4-nitrotoluene, 2,4-dinitrotoluene, respectively, which are comparable to the detecting efficiency of the state-of-the-art CMP-based sensing agents. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. Thiolate ligands for synthesis of water-soluble gold clusters.

    Science.gov (United States)

    Ackerson, Christopher J; Jadzinsky, Pablo D; Kornberg, Roger D

    2005-05-11

    Water-soluble monolayer-protected gold clusters (MPCs) have been an object of investigation by many research groups since their first syntheses were reported in 1998 and 1999. The basic requirements for a ligand to form a monolayer protecting a gold cluster were established some time ago for alkanethiolate MPCs, but there has been no such information published for water-soluble MPCs. We identify 6 new ligands capable of forming water-soluble MPCs, as well as 22 water-soluble ligands that fail to form MPCs. Our findings contribute not only to the definition of the requirements for MPC formation but also to the variety of MPCs available for applications in chemistry and biology.

  18. Ion-specific self-assembly of low-dimension aggregate structures of conjugated polymer at two-phase interface.

    Science.gov (United States)

    Zhou, Chunjie; Chen, Nan; Yang, Jien; Liu, Huibiao; Li, Yuliang

    2012-04-23

    A novel and facile approach to manipulate the morphology of Cu(2+)-ion-specific assembly of conjugated polymer by coordinative interaction at an oil-water two-phase interface is present. The application of increasing importance is the use of π-conjugated polymers as receptors, exploiting their ability to selectively form complexes, which can obviously change the optical properties in solution and induce the formation of varied solid nano/microstructures. By this method, microtubes are formed through self-rolling of a strained ionic bilayer film at the oil/water interface. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. 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.

  20. 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.

    Directory of Open Access Journals (Sweden)

    Basavaraj Siddalingappa

    Full Text Available 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.

  1. 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

  2. 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.

  3. Poly(2-oxazoline)-Antibiotic Conjugates with Penicillins.

    Science.gov (United States)

    Schmidt, Martin; Bast, Livia K; Lanfer, Franziska; Richter, Lena; Hennes, Elisabeth; Seymen, Rana; Krumm, Christian; Tiller, Joerg C

    2017-09-20

    The conjugation of antibiotics with polymers is rarely done, but it might be a promising alternative to low-molecular-weight derivatization. The two penicillins penicillin G (PenG) and penicillin V (PenV) were attached to the end groups of different water-soluble poly(2-oxazoline)s (POx) via their carboxylic acid function. This ester group was shown to be more stable against hydrolysis than the β-lactam ring of the penicillins. The conjugates are still antimicrobially active and up to 20 times more stable against penicillinase catalyzed hydrolysis. The antibiotic activity of the conjugates against Staphylococcus aureus in the presence of penicillinase is up to 350 times higher compared with the free antibiotics. Conjugates with a second antimicrobial function, a dodecyltrimethylammonium group (DDA-X), at the starting end of the PenG and PenV POx conjugates are more antimicrobially active than the conjugates without DDA-X and show high activity in the presence of penicillinase. For example, the conjugates DDA-X-PEtOx-PenG and DDA-X-PEtOx-PenV are 200 to 350 times more active against S. aureus in the presence of penicillinase and almost as effective as the penicillinase stable cloxacollin (Clox) under these conditions. These conjugates show even greater activity compared to cloxacollin without this enzyme present. Further, both conjugates kill Escherichia coli more effectively than PenG and Clox.

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

    KAUST Repository

    Lima, Igo T.

    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.

  5. Metal-Free, Multicomponent Synthesis of Pyrrole-Based π-Conjugated Polymers from Imines, Acid Chlorides, and Alkynes.

    Science.gov (United States)

    Kayser, Laure V; Vollmer, Moritz; Welnhofer, Merve; Krikcziokat, Hanna; Meerholz, Klaus; Arndtsen, Bruce A

    2016-08-24

    Multicomponent coupling reactions (MCRs) are becoming increasingly used in the synthesis of macromolecules, as they can allow the rapid generation of libraries of materials as a method to tune properties. MCRs could prove particularly useful in the synthesis of π-conjugated polymers in which structural changes are necessary for fine-tuning of electronic properties. We describe here the first metal-free multicomponent approach to conjugated polymers. This reaction exploits the coupling of imines, acid chlorides, and (catechyl)PPh to generate phospha-münchnone-containing polymers, which can be converted to poly(pyrroles) via cycloaddition. The platform allows for the efficient synthesis of families of high molecular weight polymers in one step from readily available monomers.

  6. Light-induced electron paramagnetic resonance evidence of charge transfer in electrospun fibers containing conjugated polymer/fullerene and conjugated polymer/fullerene/carbon nanotube blends

    Energy Technology Data Exchange (ETDEWEB)

    Shames, Alexander I. [Department of Physics, Ben-Gurion University of the Negev, Beersheba 84105 (Israel); Bounioux, Celine [Department of Solar Energy and Environmental Physics, Jacob Blaustein Institutes for Desert Research, Ben-Gurion University of the Negev, Sede Boker Campus 84990 (Israel); Katz, Eugene A. [Department of Solar Energy and Environmental Physics, Jacob Blaustein Institutes for Desert Research, Ben-Gurion University of the Negev, Sede Boker Campus 84990 (Israel); Ilze Katz Institute for Nanoscale Science and Technology, Ben-Gurion University of the Negev, Beer-Sheva 84105 (Israel); Yerushalmi-Rozen, Rachel [Ilze Katz Institute for Nanoscale Science and Technology, Ben-Gurion University of the Negev, Beer-Sheva 84105 (Israel); Department of Chemical Engineering, Ben-Gurion University of the Negev, Beer-Sheva 84105 (Israel); Zussman, Eyal [Department of Mechanical Engineering, Technion, Haifa 32000 (Israel)

    2012-03-12

    Electrospun sub-micron fibers containing conjugated polymer (poly(3-hexylthiophene), P3HT) with a fullerene derivative, phenyl-C61-butyric acid methylester (PCBM) or a mixture of PCBM and single-walled carbon nanotubes (SWCNTs) were studied by light-induced electron paramagnetic resonance spectroscopy. The results provide experimental evidence of electron transfer between PCBM and P3HT components in both fiber systems and suggest that the presence of a dispersing block-copolymer, which acts via physical adsorption onto the PCBM and SWCNT moieties, does not prevent electron transfer at the P3HT-PCBM interface. These findings suggest a research perspective towards utilization of fibers of functional nanocomposites in fiber-based organic optoelectronic and photovoltaic devices. The latter can be developed in the textile-type large area photovoltaics or individual fiber-based solar cells that will broaden energy applications from macro-power tools to micro-nanoscale power conversion devices and smart textiles.

  7. Light-induced electron paramagnetic resonance evidence of charge transfer in electrospun fibers containing conjugated polymer/fullerene and conjugated polymer/fullerene/carbon nanotube blends

    Science.gov (United States)

    Shames, Alexander I.; Bounioux, Céline; Katz, Eugene A.; Yerushalmi-Rozen, Rachel; Zussman, Eyal

    2012-03-01

    Electrospun sub-micron fibers containing conjugated polymer (poly(3-hexylthiophene), P3HT) with a fullerene derivative, phenyl-C61-butyric acid methylester (PCBM) or a mixture of PCBM and single-walled carbon nanotubes (SWCNTs) were studied by light-induced electron paramagnetic resonance spectroscopy. The results provide experimental evidence of electron transfer between PCBM and P3HT components in both fiber systems and suggest that the presence of a dispersing block-copolymer, which acts via physical adsorption onto the PCBM and SWCNT moieties, does not prevent electron transfer at the P3HT-PCBM interface. These findings suggest a research perspective towards utilization of fibers of functional nanocomposites in fiber-based organic optoelectronic and photovoltaic devices. The latter can be developed in the textile-type large area photovoltaics or individual fiber-based solar cells that will broaden energy applications from macro-power tools to micro-nanoscale power conversion devices and smart textiles.

  8. Influence of polymethacrylates and compritol on release profile of a highly water soluble drug metformin hydrochloride

    Directory of Open Access Journals (Sweden)

    Sunita Dahiya

    2015-01-01

    Full Text Available Aims: The present investigation studied effect of polymethacrylates Eudragit RSPO, Eudragit RLPO and compritol 888 ATO on release profile of highly water soluble drug metformin hydrochloride (MET. Materials and Methods: The solid dispersions were prepared using drug:polymer ratios 1:1 and 1:5 by coevaporation and coprecipitation techniques. Solid dispersions were characterized by infrared Spectroscopy (IR, differential scanning calorimetry (DSC, X-ray diffractometry (XRD as well as content uniformity, in vitro dissolution studies in 0.1 N HCl pH 1.2, phosphate buffer pH 6.8. Results and Discussion: Results of the studies suggested that there were progressive disappearance or changes of prominent peaks in IR, X-ray diffraction and thermotropic drug signals in coevaporates and coprecipitates with increased amount of polymers. Moreover, the in vitro release of highly water soluble MET could be extended at higher drug:polymer ratios. Conclusion: It was summarized that Eudragit RLPO had greater capacity of drug release than Eudragit RSPO and Comproitol 888 and its coevaporates in 1:5 drug:polymer ratio (F11 displayed extended drug release with comparatively higher dissolution rates (92.15 % drug release at 12 hour following near Zero order kinetics (r² =0.9822.

  9. Overcoming multidrug resistance in Dox-resistant neuroblastoma cell lines via treatment with HPMA copolymer conjugates containing anthracyclines and P-gp inhibitors.

    Science.gov (United States)

    Koziolová, Eva; Janoušková, Olga; Cuchalová, Lucie; Hvězdová, Zuzana; Hraběta, Jan; Eckschlager, Tomáš; Sivák, Ladislav; Ulbrich, Karel; Etrych, Tomáš; Šubr, Vladimír

    2016-07-10

    Water-soluble N-(2-hydroxypropyl)methacrylamide copolymer conjugates bearing the anticancer drugs doxorubicin (Dox) or pirarubicin (THP), P-gp inhibitors derived from reversin 121 (REV) or ritonavir (RIT)), or both anticancer drug and P-gp inhibitor were designed and synthesized. All biologically active molecules were attached to the polymer carrier via pH-sensitive spacer enabling controlled release in mild acidic environment modeling endosomes and lysosomes of tumor cells. The cytotoxicity of the conjugates against three sensitive and Dox-resistant neuroblastoma (NB) cell lines, applied alone or in combination, was studied in vitro. All conjugates containing THP displayed higher cytotoxicity against all three Dox-resistant NB cell lines compared with the corresponding Dox-containing conjugates. Furthermore, the cytotoxicity of conjugates containing both drug and P-gp inhibitor was up to 10 times higher than that of the conjugate containing only drug. In general, the polymer-drug conjugates showed higher cytotoxicity when conjugates containing inhibitors were added 8 or 16h prior to treatment compared with conjugates bearing both the inhibitor and the drug. The difference in cytotoxicity was more pronounced at the 16-h time point. Moreover, higher inhibitor:drug ratios resulted in higher cytotoxicity. The cytotoxicity of the polymer-drug used in combination with polymer P-gp inhibitor was up to 84 times higher than that of the polymer-drug alone. Copyright © 2016 Elsevier B.V. All rights reserved.

  10. Synthesis, characterization, and antiplasmodial activity of polymer-incorporated aminoquinolines.

    Science.gov (United States)

    Aderibigbe, B A; Neuse, E W; Sadiku, E R; Ray, S Shina; Smith, P J

    2014-06-01

    In this research, aminoquinoline compounds were synthesized, characterized, and incorporated into water-soluble polymers to form conjugates. The conjugates were characterized by X-ray diffraction, thermal gravimetric analysis, scanning electron microscope, Fourier transform infrared spectroscopy, and nuclear magnetic resonance spectroscopy to confirm the successful incorporation of the aminoquinoline compound on to the polymer. The synthesized conjugates were screened for in vitro antiplasmodial activity in triplet test against chloroquine-sensitive strain of Plasmodium falciparum and chloroquine drug was used as a reference drug in all the experiments. A full dose-response was performed to determine the concentration inhibiting 50% of parasite growth (IC50 value). Polymeric conjugates containing 3-diethylamino-1-propylamine solubilizing units were found to be most active against the chloroquine-sensitive strain of P. falciparum. © 2013 Wiley Periodicals, Inc.

  11. 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.

  12. Functionalization of emissive conjugated polymer nanoparticles by coprecipitation: consequences for particle photophysics and colloidal properties.

    Science.gov (United States)

    Singh, Amita; Bezuidenhout, Michael; Walsh, Nichola; Beirne, Jason; Felletti, Riccardo; Wang, Suxiao; Fitzgerald, Kathleen T; Gallagher, William M; Kiely, Patrick; Redmond, Gareth

    2016-07-29

    The functionalization of polyfluorene (PFO) nanoparticles by coprecipitation of the conjugated polymer with an amphiphilic comb polymer, consisting of a hydrophobic polystyrene backbone with hydrophilic, carboxylic acid-terminated polyethylene oxide side-chains (PS-PEG-COOH), is investigated. The comb polymer affects the properties of the formed hybrid nanoparticles. Non-functionalized particles are typically larger (28 nm) than functionalized ones (20 nm); peak molar extinction coefficients are found to differ in a similar trend. Zeta potentials are negative, consistent with negative surface charge on PFO particles due to chemical defect formation, with additional charge on functionalized particles due to the pendant carboxylic acid groups. Emission quantum yields of functionalized particles are typically larger, consistent with lower efficiency of energy transfer to quenchers in smaller particles and weaker PFO interchain interactions due to chain dilution. The trend in per-particle fluorescence brightness values, as confirmed by single particle fluorescence imaging, reflects the nanoparticle extinction coefficients. Photostability studies on aqueous dispersions of hybrid particles indicate mild photobrightening under continuous illumination while PFO particles exhibit slow exponential emission decay. Functionalized particles are also resistant to aggregation during exposure to adenocarcinoma cells. Generally, the hybrid particles exhibit more favorable time-, pH- and medium-dependent stabilities, likely due to steric and electrostatic stabilization by PEG-carboxylic acid functionalities. Overall, the functionalized particles exhibit attractive properties: Reasonably small size, tight size distribution, high absorption cross section, radiative rate and emission quantum yield, excellent brightness and photostability, and good colloidal stability.

  13. Electrical Conductivity Studies on Individual Conjugated Polymer Nanowires: Two-Probe and Four-Probe Results

    Directory of Open Access Journals (Sweden)

    Duvail JeanLuc

    2009-01-01

    Full Text Available Abstract Two- and four-probe electrical measurements on individual conjugated polymer nanowires with different diameters ranging from 20 to 190 nm have been performed to study their conductivity and nanocontact resistance. The two-probe results reveal that all the measured polymer nanowires with different diameters are semiconducting. However, the four-probe results show that the measured polymer nanowires with diameters of 190, 95–100, 35–40 and 20–25 nm are lying in the insulating, critical, metallic and insulting regimes of metal–insulator transition, respectively. The 35–40 nm nanowire displays a metal–insulator transition at around 35 K. In addition, it was found that the nanocontact resistance is in the magnitude of 104Ω at room temperature, which is comparable to the intrinsic resistance of the nanowires. These results demonstrate that four-probe electrical measurement is necessary to explore the intrinsic electronic transport properties of isolated nanowires, especially in the case of metallic nanowires, because the metallic nature of the measured nanowires may be coved by the nanocontact resistance that cannot be excluded by a two-probe technique.

  14. Functionalization of emissive conjugated polymer nanoparticles by coprecipitation: consequences for particle photophysics and colloidal properties

    Science.gov (United States)

    Singh, Amita; Bezuidenhout, Michael; Walsh, Nichola; Beirne, Jason; Felletti, Riccardo; Wang, Suxiao; Fitzgerald, Kathleen T.; Gallagher, William M.; Kiely, Patrick; Redmond, Gareth

    2016-07-01

    The functionalization of polyfluorene (PFO) nanoparticles by coprecipitation of the conjugated polymer with an amphiphilic comb polymer, consisting of a hydrophobic polystyrene backbone with hydrophilic, carboxylic acid-terminated polyethylene oxide side-chains (PS-PEG-COOH), is investigated. The comb polymer affects the properties of the formed hybrid nanoparticles. Non-functionalized particles are typically larger (28 nm) than functionalized ones (20 nm); peak molar extinction coefficients are found to differ in a similar trend. Zeta potentials are negative, consistent with negative surface charge on PFO particles due to chemical defect formation, with additional charge on functionalized particles due to the pendant carboxylic acid groups. Emission quantum yields of functionalized particles are typically larger, consistent with lower efficiency of energy transfer to quenchers in smaller particles and weaker PFO interchain interactions due to chain dilution. The trend in per-particle fluorescence brightness values, as confirmed by single particle fluorescence imaging, reflects the nanoparticle extinction coefficients. Photostability studies on aqueous dispersions of hybrid particles indicate mild photobrightening under continuous illumination while PFO particles exhibit slow exponential emission decay. Functionalized particles are also resistant to aggregation during exposure to adenocarcinoma cells. Generally, the hybrid particles exhibit more favorable time-, pH- and medium-dependent stabilities, likely due to steric and electrostatic stabilization by PEG-carboxylic acid functionalities. Overall, the functionalized particles exhibit attractive properties: Reasonably small size, tight size distribution, high absorption cross section, radiative rate and emission quantum yield, excellent brightness and photostability, and good colloidal stability.

  15. 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.

  16. Highly Sensitive Flexible NH3 Sensors Based on Printed Organic Transistors with Fluorinated Conjugated Polymers.

    Science.gov (United States)

    Nketia-Yawson, Benjamin; Jung, A-Ra; Noh, Yohan; Ryu, Gi-Seong; Tabi, Grace Dansoa; Lee, Kyung-Koo; Kim, BongSoo; Noh, Yong-Young

    2017-03-01

    Understanding the sensing mechanism in organic chemical sensors is essential for improving the sensing performance such as detection limit, sensitivity, and other response/recovery time, selectivity, and reversibility for real applications. Here, we report a highly sensitive printed ammonia (NH3) gas sensor based on organic thin film transistors (OTFTs) with fluorinated difluorobenzothiadiazole-dithienosilole polymer (PDFDT). These sensors detected NH3 down to 1 ppm with high sensitivity (up to 56%) using bar-coated ultrathin (NH3 interactions comprise hydrogen bonds and electrostatic interactions between the PDFDT polymer backbone and NH3 gas molecules, thus lowering the highest occupied molecular orbital levels, leading to hole trapping in the OTFT sensors. Additionally, density functional theory calculations show that gaseous NH3 molecules are captured via cooperation of fluorine atoms and dithienosilole units in PDFDT. We verified that incorporation of functional groups that interact with a specific gas molecule in a conjugated polymer is a promising strategy for producing high-performance printed OTFT gas sensors.

  17. Survey on synthesis and reaction of environmentally benign water-soluble metal complex catalysts; Kankyo chowagata suiyosei sakutai shokubai no gosei hanno no chosa

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    1997-03-01

    This report describes the research trend survey results on the synthesis and reaction of water-soluble metal complexes which are regarded as environmentally benign catalysts. For the synthesis and catalysis of water-soluble complexes, synthetic methods of water-soluble phosphines, such as sulfonated TPPMS and TPPTS, are described in detail. Synthesis and reactivity of hydroxymethylphosphines are introduced, and the application of electrospray mass spectroscopy is elucidated as a tool for the analysis of them. Changes of the application of transition metal complexes with water-soluble phosphines to catalysis are described. Dual catalysts which have both functions of phase transfer catalysts and homogeneous catalysts are introduced. Concept of counter phase transfer catalysts is also introduced, and some catalytic reactions are described. In addition, this report introduces catalysis of water-soluble polymer-supported metal complexes, immobilization of metal colloids with water-soluble ligands and their analysis, and water-soluble complexes as hybrid catalysts. 144 refs., 94 figs., 10 tabs.

  18. Enhanced water-solubility and antibacterial activity of novel chitosan derivatives modified with quaternary phosphonium salt.

    Science.gov (United States)

    Zhu, Dan; Cheng, Honghao; Li, Jianna; Zhang, Wenwen; Shen, Yuanyuan; Chen, Shaojun; Ge, Zaochuan; Chen, Shiguo

    2016-04-01

    Chitosan (CS) has been widely recognized as an important biomaterial due to its good antimicrobial activity, biocompatibility and biodegradability. However, CS is insoluble in water in neutral and alkaline aqueous solution due to the linear aggregation of chain molecules and the formation of crystallinity. This is one of the key factors that limit its practical applications. Therefore, improving the solubility of CS in neutral and alkaline aqueous solution is a primary research direction for biomedical applications. In this paper, a reactive antibacterial compound (4-(2,5-Dioxo-pyrrolidin-1-yloxycarbonyl)-benzyl)-triphenyl-phosphonium bromide (NHS-QPS) was synthesized for chemical modification of CS, and a series of novel polymeric antimicrobial agents, N-quaternary phosphonium chitosan derivatives (N-QPCSxy, x=1-2,y=1-4) were obtained. The water solubilities and antibacterial activities of N-QPCSxy against Escherichia coli and Staphylococcus aureus were evaluated compare to CS. The water solubility of N-QPCSxy was all better than that of CS at neutral pH aqueous solution, particularly, N-QPCS14 can be soluble in water over the pH range of 3 to 12. The antibacterial activities of CS derivatives were improved by introducing quaternary phosphonium salt, and antibacterial activity of N-QPCSxy increases with degree of substitution. Overall, N-QPCS14 represents a novel antibacterial polymer material with good antibacterial activity, waters solubility and low cytotoxicity. Copyright © 2015 Elsevier B.V. All rights reserved.

  19. Printable highly conductive conjugated polymer sensitized ZnO NCs as cathode interfacial layer for efficient polymer solar cells.

    Science.gov (United States)

    Liu, Jian; Wu, Jiang; Shao, Shuyan; Deng, Yunfeng; Meng, Bin; Xie, Zhiyuan; Geng, Yanhou; Wang, Lixiang; Zhang, Fengling

    2014-06-11

    We report a facile way to produce printable highly conductive cathode interfacial layer (CIL) for efficient polymer solar cells (PSCs) by sensitizing ZnO nanocrystals (NCs) with a blue fluorescent conjugated polymer, poly(9, 9-bis-(6'-diethoxylphosphorylhexyl) fluorene) (PFEP). Herein, PFEP plays dual distinctive roles in the composite. Firstly, PFEP chains can effectively block the aggregation of ZnO NCs, leading to uniform and smooth film during solution processing via assembly on ZnO NC surfaces through their pending phosphonate groups. Secondly, PFEP can greatly improve the conductivity of ZnO NCs by charge transfer doping, that is the charge transfer from the sensitizer driven by electron-chemical potential equilibrium, which could be even more pronounced under light illumination because of light excitation of PFEP sensitizer. The increased conductivity in ZnO-PFEP layer renders more efficient electron transport and extraction compared to pristine ZnO layer. This ZnO-PFEP CIL was successfully applied to PSCs based on three polymer donor systems with different band-gaps, and efficiency enhancements from 44 to 70% were observed compared to those PSCs with pristine ZnO CIL. The highest efficiency of 7.56% was achieved in P(IID-DTC):PC70BM-based PSCs by using ZnO-PFEP film as CIL. Moreover, the enhanced conductivity due to the charge-transfer doping effect allows thick ZnO-PFEP film to be used as CIL in high-performance PSCs. Both the high conductivity and good film-forming properties of ZnO-PFEP CIL are favorable for large-scale printable PSCs, which is also verified by high-efficiency PSCs with ZnO-PFEP CIL fabricated using doctor-blading, a large-scale processing technique. The work provides an efficient printable cathode interfacial material for efficient PSCs.

  20. Using Molecular Simulations to Link Chemical and Physical Features of Conjugated Polymers and Fullerene Derivatives to Bulk Heterojunction Morphology for Organic Photovoltaics

    Science.gov (United States)

    Marsh, Hilary; Jankowski, Eric; Jayaraman, Arthi

    2014-03-01

    The morphology of blends of conjugated polymers (electron donors) and fullerene derivatives (electron acceptors) strongly affects the charge transport, charge separation and the overall efficiency of organic photovoltaic devices. In this talk we will present coarse-grained molecular simulation studies to understand how molecular-level features such as alkyl side chain length, alkyl side chain spacing along thiophene polymer backbone and fullerene functionalization (and in turn miscibility with the conjugated polymer) affect the blend morphology. Our coarse-grained models are validated by reproducing neat polymer (without acceptors) morphologies observed in experiments, such as lamellae and hexagonally packed cylinders. Furthermore, for blends of conjugated polymers and fullerene derivatives, this work shows how conjugated polymer architecture and acceptor miscibility can be tuned to obtain new blend morphologies with features that are known to enhance efficiency of organic solar cells.

  1. Resonance Raman investigation of β-cyclodextrin-encapsulated π-conjugated polymers.

    Science.gov (United States)

    Kasiouli, Soulianna; Di Stasio, Francesco; McDonnell, Shane O; Constantinides, Christos P; Anderson, Harry L; Cacialli, Franco; Hayes, Sophia C

    2013-05-09

    Resonance Raman (RR) spectroscopy is used to investigate the effect of β-cyclodextrin encapsulation on the structural and photophysical properties of poly(4,4'-diphenylenevinylene). We especially focus on the thermal stability of the polymer. We find that within the range of 10-55 °C the uninsulated polymer exhibits decreased Raman intensity in all the vibrational bands with temperature, along with changes in the relative intensity of the C-C inter-ring stretch mode at 1270 cm(-1) with respect to the ring C-H in-plane symmetric bend at 1187 cm(-1), which provides evidence for conformational changes as a function of temperature. No changes are observed in the intensity of the in-phase CH out-of-plane wag of the vinylene group at 968 cm(-1). Therefore, the conformational changes involve mainly dihedral angle modification between the adjacent phenyl rings toward planarization, and little or no change in the planarity of the trans-vinylene group. The decrease of the optical absorption at 55 °C with respect to that at room temperature and the appearance of a new absorption band at lower energies explain the decrease in the RR intensities and the wavelength dependence of the relative intensities of the Raman band. We note that the conformational change into a more planar geometry, which affects a significant portion of the polymer population, is irreversible and consistent with thermally induced aggregation. Such a planarization is unexpected in view of the usually observed thermochromic behavior of conjugated polymers, which leads to an increase of the energy gap for increasing temperature, as the average dihedral angles are increased due to excitation of a larger number of vibrational modes. Interestingly, the higher threading ratio polymers are resistant to any conformational changes within this temperature range, as reflected by their unchanged RR spectra, due to the rotaxane's ability to suppress intermolecular interactions and aggregation. Interestingly, the

  2. Ratiometric Array of Conjugated Polymers-Fluorescent Protein Provides a Robust Mammalian Cell Sensor.

    Science.gov (United States)

    Rana, Subinoy; Elci, S Gokhan; Mout, Rubul; Singla, Arvind K; Yazdani, Mahdieh; Bender, Markus; Bajaj, Avinash; Saha, Krishnendu; Bunz, Uwe H F; Jirik, Frank R; Rotello, Vincent M

    2016-04-06

    Supramolecular complexes of a family of positively charged conjugated polymers (CPs) and green fluorescent protein (GFP) create a fluorescence resonance energy transfer (FRET)-based ratiometric biosensor array. Selective multivalent interactions of the CPs with mammalian cell surfaces caused differential change in FRET signals, providing a fingerprint signature for each cell type. The resulting fluorescence signatures allowed the identification of 16 different cell types and discrimination between healthy, cancerous, and metastatic cells, with the same genetic background. While the CP-GFP sensor array completely differentiated between the cell types, only partial classification was achieved for the CPs alone, validating the effectiveness of the ratiometric sensor. The utility of the biosensor was further demonstrated in the detection of blinded unknown samples, where 121 of 128 samples were correctly identified. Notably, this selectivity-based sensor stratified diverse cell types in minutes, using only 2000 cells, without requiring specific biomarkers or cell labeling.

  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. Conjugated polymer-fullerene blend with strong optical limiting in the near-infrared.

    Science.gov (United States)

    Chi, San-Hui; Hales, Joel M; Cozzuol, Matteo; Ochoa, Charles; Fitzpatrick, Madison; Perry, Joseph W

    2009-11-23

    Optical-quality, melt processable thick films of a conjugated polymer blend containing poly(2-methoxy-5-(2-ethyl-hexyloxy)-(phenylene vinylene)) (MEH-PPV), a C(60) derivative (PCBM) and a plasticizer (1,2-di-iso-octylphthalate) have been developed and their nonlinear absorption and optical limiting properties have been investigated. These blend materials exhibited strong optical limiting characteristics in the near infrared region (750-900 nm), with broad temporal dynamic range spanning femtosecond to nanosecond pulse widths. The dispersion of the optical limiting figure-of-merit of the MEH-PPV:PCBM:DOP blend shows a peak near the wavelength of the MEH-PPV cation, indicating an important role of one-photon and two-photon induced charge transfer in the nonlinear absorption response.

  5. Photoresponsive Conjugated Microporous Polymer Films Fabricated by Electrochemical Deposition for Controlled Release.

    Science.gov (United States)

    Zhao, Ruiyang; Han, Jishu; Huang, Mei; Liu, Fusheng; Wang, Lei; Ma, Yuguang

    2017-09-01

    Stable controlled release system, conjugated microporous polymers (CMPs) with stimuli-responsive properties can be ideal structures because their 3D microporous matrix structure and possible stimulated response provide inherent switchable acceptor sites to capture and release guest molecules. Herein, the in situ electrochemical deposition of precursors (DTCzAzo) is utilized to construct highly crosslinked photoresponsive CMP films, which can reversibly undergo the trans-to-cis isomerization alternately with irradiation by 355 and 480 nm laser beams. The size of pores in CMP films changes tremendously during the process of trans-cis photoisomerization, to controllably capture, conserve, and release the guest molecules. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. Anti-Lymphoma Efficacy Comparison of Anti-Cd20 Monoclonal Antibody-Targeted and Non-Targeted Star-Shaped Polymer-Prodrug Conjugates.

    Science.gov (United States)

    Lidický, Ondřej; Janoušková, Olga; Strohalm, Jiří; Alam, Mahmudul; Klener, Pavel; Etrych, Tomáš

    2015-11-04

    Here we describe the synthesis and biological properties of two types of star-shaped polymer-doxorubicin conjugates: non-targeted conjugate prepared as long-circulating high-molecular-weight (HMW) polymer prodrugs with a dendrimer core and a targeted conjugate with the anti-CD20 monoclonal antibody (mAb) rituximab (RTX). The copolymers were linked to the dendrimer core or to the reduced mAb via one-point attachment forming a star-shaped structure with a central antibody or dendrimer surrounded by hydrophilic polymer chains. The anticancer drug doxorubicin (DOX) was attached to the N-(2-hydroxypropyl)methacrylamide (HPMA)-based copolymer chain in star polymer systems via a pH-labile hydrazone linkage. Such polymer-DOX conjugates were fairly stable in aqueous solutions at pH 7.4, and the drug was readily released in mildly acidic environments at pH 5-5.5 by hydrolysis of the hydrazone bonds. The cytotoxicity of the polymer conjugates was tested on several CD20-positive or negative human cell lines. Similar levels of in vitro cytotoxicity were observed for all tested polymer conjugates regardless of type or structure. In vivo experiments using primary cell-based murine xenograft models of human diffuse large B-cell lymphoma confirmed the superior anti-lymphoma efficacy of the polymer-bound DOX conjugate when compared with the original drug. Targeting with RTX did not further enhance the anti-lymphoma efficacy relative to the non-targeted star polymer conjugate. Two mechanisms could play roles in these findings: changes in the binding ability to the CD-20 receptor and a significant loss of the immunological properties of RTX in the polymer conjugates.

  7. Anti-Lymphoma Efficacy Comparison of Anti-Cd20 Monoclonal Antibody-Targeted and Non-Targeted Star-Shaped Polymer-Prodrug Conjugates

    Directory of Open Access Journals (Sweden)

    Ondřej Lidický

    2015-11-01

    Full Text Available Here we describe the synthesis and biological properties of two types of star-shaped polymer-doxorubicin conjugates: non-targeted conjugate prepared as long-circulating high-molecular-weight (HMW polymer prodrugs with a dendrimer core and a targeted conjugate with the anti-CD20 monoclonal antibody (mAb rituximab (RTX. The copolymers were linked to the dendrimer core or to the reduced mAb via one-point attachment forming a star-shaped structure with a central antibody or dendrimer surrounded by hydrophilic polymer chains. The anticancer drug doxorubicin (DOX was attached to the N-(2-hydroxypropylmethacrylamide (HPMA-based copolymer chain in star polymer systems via a pH-labile hydrazone linkage. Such polymer-DOX conjugates were fairly stable in aqueous solutions at pH 7.4, and the drug was readily released in mildly acidic environments at pH 5–5.5 by hydrolysis of the hydrazone bonds. The cytotoxicity of the polymer conjugates was tested on several CD20-positive or negative human cell lines. Similar levels of in vitro cytotoxicity were observed for all tested polymer conjugates regardless of type or structure. In vivo experiments using primary cell-based murine xenograft models of human diffuse large B-cell lymphoma confirmed the superior anti-lymphoma efficacy of the polymer-bound DOX conjugate when compared with the original drug. Targeting with RTX did not further enhance the anti-lymphoma efficacy relative to the non-targeted star polymer conjugate. Two mechanisms could play roles in these findings: changes in the binding ability to the CD-20 receptor and a significant loss of the immunological properties of RTX in the polymer conjugates.

  8. Water soluble heterometallic potassium-dioxidovanadium(V) complexes as potential antiproliferative agents.

    Science.gov (United States)

    Sutradhar, Manas; Fernandes, Alexandra R; Silva, Joana; Mahmudov, Kamran T; Guedes da Silva, M Fátima C; Pombeiro, Armando J L

    2016-02-01

    Two water soluble heterometallic potassium–dioxidovanadium polymers, [KVO2(L1)]n (1) and [KVO2(L2)(H2O)]n (2) [H2L1= (2,3-dihydroxybenzylidene)-2-hydroxybenzohydrazide and H2L2=(2,3-dihydroxybenzylidene)benzohydrazide], have been synthesized and characterized by IR, NMR, elemental analysis and single crystal X-ray diffraction. The antiproliferative potentials of 1 and 2 were examined towards human colorectal carcinoma (HCT116), and lung (A549) and breast (MCF7) adenocarcinoma cell lines. 1 exhibits a high cytotoxic activity against colorectal carcinoma cells (HCT116), with IC50 lower than those for cisplatin.

  9. 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

  10. Nanostructures of an amphiphilic zinc phthalocyanine polymer conjugate for photodynamic therapy of psoriasis.

    Science.gov (United States)

    Jin, Yiguang; Zhang, Xiaohan; Zhang, Baolei; Kang, Hongxiang; Du, Lina; Li, Miao

    2015-04-01

    Psoriasis is a chronic inflammatory skin disease affecting 2-5% of the population worldwide and it severely affects patient quality of life. In this study, an amphiphilic zinc phthalocyanine polymer conjugate (ZPB) was synthesized, in which zinc phthalocyanine (ZnPc) was conjugated with the poly(ethylene glycol) (PEG) chain of Brij 58. ZPB showed two maximum UV-vis absorption wavelengths, 348 nm and 678 nm. A monomolecular micelle of ZPB formed in water with a mean size of 25 nm and zeta potential of -15 mV. The nanostructures aggregated into cloudy precipitates, which were easily dispersed. The nanostructure showed the shell-core structure with the ZnPc segments as the core and the PEG chains as the shell. The anti-psoriasis effect of the ZPB nanostructure was explored using a guinea pig psoriasis model. After comparing the anti-psoriasis effects of saline, light alone, ZPB alone, and the combination of light and ZPB, the combination of light and ZPB showed the best photodynamic therapy of psoriasis based on the light excitation of the photosensitizer ZPB and the psoriasis was nearly cured according to the histopathological investigation. The ZPB nanostructure is a promising anti-psoriasis nanomedicine based on photodynamic therapy. Copyright © 2015 Elsevier B.V. All rights reserved.

  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. 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

  13. 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.

  14. 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%.

  15. Preparation and Chemical Properties of π-Conjugated Polymers Containing Indigo Unit in the Main Chain

    Directory of Open Access Journals (Sweden)

    Hiroki Fukumoto

    2014-03-01

    Full Text Available π-Conjugated polymers based on indigo unit were prepared. Dehalogenative polycondensation of N-hexyl-6,6'-dibromoindigo with a zerovalent nickel complex gave a homopolymer, P(HexI, in 77% yield. Copolymer of N-hexyl-indigo and pyridine, P(HexI-Py, was also prepared in 50% yield. P(HexI showed good solubility in organic solvents, whereas P(HexI-Py was only soluble in acids such as HCOOH. The weight-average molecular weights (Mw of P(HexI and P(HexI-Py were determined to be 10,000 and 40,000, respectively, by a light scattering method. Pd-catalyzed polycondensation between 6,6'-dibromoindigo with N-BOC (BOC = t-butoxycarbonyl substituents and a diboronic compound of 9,9-dioctylfluorene afforded the corresponding alternating copolymer, P(BOCI-Flu, as a deep red solid in 98% yield. P(BOCI-Flu was soluble in N-methyl-2-pyrroridone and showed an Mw of 29,000 in GPC analysis. Treatment of P(BOCI-Flu with CF3COOH smoothly led to a BOC-deprotection reaction to give an insoluble deep green polymer, P(I-Flu, in a quantitative yield. Diffuse reflectance spectra of powdery P(BOCI-Flu and P(I-Flu showed peaks at about 580 nm and 630 nm, respectively, which are thought to originate from the indigo unit.

  16. Mimicking conjugated polymer thin-film photophysics with a well-defined triblock copolymer in solution.

    Science.gov (United States)

    Brazard, Johanna; Ono, Robert J; Bielawski, Christopher W; Barbara, Paul F; Vanden Bout, David A

    2013-04-25

    Conjugated polymers (CPs) are promising materials for use in electronic applications, such as low-cost, easily processed organic photovoltaic (OPV) devices. Improving OPV efficiencies is hindered by a lack of a fundamental understanding of the photophysics in CP-based thin films that is complicated by their heterogeneous nanoscale morphologies. Here, we report on a poly(3-hexylthiophene)-block-poly(tert-butyl acrylate)-block-poly(3-hexylthiophene) rod-coil-rod triblock copolymer. In good solvents, this polymer resembles solutions of P3HT; however, upon the addition of a poor solvent, the two P3HT chains within the triblock copolymer collapse, affording a material with electronic spectra identical to those of a thin film of P3HT. Using this new system as a model for thin films of P3HT, we can attribute the low fluorescence quantum yield of films to the presence of a charge-transfer state, providing fundamental insights into the condensed phase photophysics that will help to guide the development of the next generation of materials for OPVs.

  17. 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.

  18. 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.

  19. 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.

  20. HPMA copolymer conjugates of paclitaxel and docetaxel with pH-controlled drug release.

    Science.gov (United States)

    Etrych, Tomás; Sírová, Milada; Starovoytova, L; Ríhová, Blanka; Ulbrich, Karel

    2010-08-02

    In this paper we describe the synthesis, physicochemical characteristics and data on the biological activity of polymer prodrugs based on the anticancer drugs paclitaxel (PTX) and docetaxel (DTX) conjugated with a water-soluble N-(2-hydroxypropyl)methacrylamide (HPMA) copolymer drug carrier. The drugs were derivatized and then attached to the polymer backbone via a spacer that is stable under physiological conditions (pH 7.4) and hydrolytically degradable in mild acidic environments (e.g., endosomes, pH approximately 5). Polymer-drug conjugates were designed to achieve prolonged blood circulation and release of the active compound in target cells. Six types of conjugates differing in the structure of the keto acid (levulic, 3-(acetyl)acrylic acid) and 4-(2-oxopropyl)benzoic acid-containing spacer or in the amount of drug bound to the HPMA copolymer were synthesized. In all the conjugates, the linkage susceptible to hydrolytic cleavage was formed by the reaction of the carbonyl group of a drug derivative with the hydrazide group-terminated side chains of the polymer. In vitro incubation of the conjugates in buffers resulted in much faster release of drugs or their derivatives from the polymer at pH 5 than at pH 7.4 with the rate depending on the detailed structure of the spacer. Conjugates containing drugs acylated with levulic acid were tested for their anticancer activity in vivo using two murine models. The PTX-containing conjugate showed better antitumor efficacy in the 4T1 model of mammary carcinoma than the parent drug and its derivative. The DTX-containing conjugate demonstrated high activity in treating EL4 T cell lymphoma. The treatment with the polymer conjugates was devoid of side toxicity. In both models, we achieved complete regression of established tumors accompanied by a durable tumor resistance in most of the cured animals.

  1. pi-Conjugated chelating polymers with charged iridium complexes in the backbones: synthesis, characterization, energy transfer, and electrochemical properties.

    Science.gov (United States)

    Liu, Shu-Juan; Zhao, Qiang; Chen, Run-Feng; Deng, Yun; Fan, Qu-Li; Li, Fu-You; Wang, Lian-Hui; Huang, Chun-Hui; Huang, Wei

    2006-05-24

    A series of pi-conjugated chelating polymers with charged iridium (Ir) complexes in the backbones were synthesized by a Suzuki polycondensation reaction, leading to homogeneous polymeric materials that phosphoresce red light. The fluorene and bipyridine (bpy) segments were used as polymer backbones. 5,5'-Dibromobipyridine served as a ligand to form a charged iridium complex monomer with 1-(9'9-dioctylfluorene-2-yl)isoquinoline (Fiq) as the cyclometalated ligand. Chemical and photophysical characterization confirmed that Ir complexes were incorporated into the backbones as one of the repeat units by means of the 5,5'-dibromobipyridine ligand. Chelating polymers showed almost complete energy transfer from the host fluorene segments to the guest Ir complexes in the solid state when the feed ratio was 2 mol %. In the films of the corresponding blend system, however, energy transfer was not complete even when the content of Ir complexes was as high as 16 mol %. Both intra- and intermolecular energy-transfer processes existed in this host-guest system, and the intramolecular energy transfer was a more efficient process. All chelating polymers displayed good thermal stability, redox reversibility, and film formation. These chelating polymers also showed more efficient energy transfer than the corresponding blended system and the mechanism of incorporation of the charged Ir complexes into the pi-conjugated polymer backbones efficiently avoided the intrinsic problems associated with the blend system, thus offering promise in optoelectronic applications.

  2. 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 (polymer nanoparticle surfactant stabilizer used determine particle internalization and biocompatibility profile.

  3. Conjugated Polymer based sensor for detecting explosives such as RDX (1,3,5-Trinitroperhydro-1,3,5-triazine)

    Science.gov (United States)

    Kumar, Abhishek; Anandkathir, Robinson; Kumar, Jayant

    2009-03-01

    Conjugated polymers are an important class of materials and have attracted great scientific interests because of their unique optical and electrical properties. Synthesis of various conjugated polymers has been reported for detecting DNT and TNT. Here, for the first time, we report the synthesis and characterization of a conjugated polymer based on thiophene, Poly[2-(3-thienyl)ethanol n-butoxycarbonylmethylurethane] (PURET), for the detection of RDX via fluorescence quenching. The incorporation of judiciously chosen bulky butoxycarbonylmethyl urethane side group in the back bone of polythiophene reduces the aggregation, improves the solubility of the polymer in the organic solvents and quantum yield of fluorescence. We have observed a 15 % decrease of fluorescence in 60 sec in thin films of PURET exposed to the saturated vapor of RDX at room temperature. The large exciton diffusion length and interaction between side group and the quencher molecule are believed to be the reasons for enhanced RDX detection. Sensitivity below 5 parts per trillion (ppt) has been demonstrated for RDX at room temperature. The effect of nanostructures (electrospun nanofibers and stamped 1 D periodic pattern) on sensitivity and response time will also be discussed.

  4. Shell thickness dependent photoinduced hole transfer in hybrid conjugated polymer/quantum dot nanocomposites: from ensemble to single hybrid level.

    Science.gov (United States)

    Xu, Zhihua; Hine, Corey R; Maye, Mathew M; Meng, Qingping; Cotlet, Mircea

    2012-06-26

    Photoinduced hole transfer is investigated in inorganic/organic hybrid nanocomposites of colloidal CdSe/ZnS quantum dots and a cationic conjugated polymer, poly(9,9'-bis(6-N,N,N-trimethylammoniumhexyl)fluorene-alt-phenylene, in solution and in solid thin film, and down to the single hybrid level and is assessed to be a dynamic quenching process. We demonstrate control of hole transfer rate in these quantum dot/conjugated polymer hybrids by using a series of core/shell quantum dots with varying shell thickness, for which a clear exponential dependency of the hole transfer rate vs shell thickness is observed, for both solution and thin-film situations. Furthermore, we observe an increase of hole-transfer rate from solution to film and correlate this with changes in quantum dot/polymer interfacial morphology affecting the hole transfer rate, namely, the donor-acceptor distance. Single particle spectroscopy experiments reveal fluctuating dynamics of hole transfer at the single conjugated polymer/quantum dot interface and an increased heterogeneity in the hole-transfer rate with the increase of the quantum dot's shell thickness. Although hole transfer quenches the photoluminescence intensity of quantum dots, it causes little or no effect on their blinking behavior over the time scales probed here.

  5. Plasma concentrations of water.soluble vitamins in metabolic ...

    African Journals Online (AJOL)

    Context: Vitamins B1 (thiamine), B3 (niacin), B6 (pyridoxine), and C (ascorbic acid) are vital for energy, carbohydrate, lipid, and amino acid metabolism and in the regulation of the cellular redox state. Some studies have associated low levels of water.soluble vitamins with metabolic syndrome and its various components.

  6. Plasma concentrations of water-soluble vitamins in metabolic ...

    African Journals Online (AJOL)

    2012-01-21

    Jan 21, 2012 ... levels of water-soluble vitamins with metabolic syndrome and its various components. Aims: This study aims to determine the plasma concentrations of vitamins B1, B3, B6, and C in Nigerians with metabolic syndrome and in healthy controls. Settings and Design: One-hundred subjects with metabolic ...

  7. Synthesis and characterization of water-soluble carbon nanotubes ...

    Indian Academy of Sciences (India)

    Carbon nanotubes (CNT) has been synthesized by pyrolysing mustard oil using an oil lamp. It was made water-soluble (wsCNT) through oxidative treatment by dilute nitric acid and was characterized by SEM, AFM, XRD, Raman and FTIR spectroscopy. The synthesized wsCNT showed the presence of several junctions and ...

  8. Water-soluble diphosphadiazacyclooctanes as ligands for aqueous organometallic catalysis

    KAUST Repository

    Boulanger, Jérôme

    2012-12-01

    Two new water-soluble diphosphacyclooctanes been synthesized and characterized by NMR and surface tension measurements. Both phosphanes proved to coordinate rhodium in a very selective way as well-defined bidentates were obtained. When used in Rh-catalyzed hydroformylation of terminal alkenes, both ligands positively impacted the reaction chemoselectivity. © 2012 Elsevier B.V.

  9. Seasonal and genotypic variation of water-soluble polysaccharide ...

    African Journals Online (AJOL)

    Cyclocarya paliurus (Batal) Iljinskaja is an important medicinal woody plant due to numerous bioactive natural products in its leaves. As an important bioactive natural product, water-soluble polysaccharides (WSP) in leaves of C. paliurus possess diverse biological activities, such as hypoglycemic, anticancer and ...

  10. Bioremediation prospects of fungi isolated from water soluble ...

    African Journals Online (AJOL)

    Bioremediation prospects of fungi isolated from water soluble fraction of crude oil samples. ... the level of pH, EC and TDS. The ability of the fungi to adapt to these conditions indicates their potential as a tool for bioremediation of crude oil polluted water. Keywords: Bioremediation, Crude Oil, Fungi, Polluted Water, Potential.

  11. SYNTHESIS AND PROPERTIES OF STERICALLY HINDERED WATER SOLUBLE PORPHYRINE

    Directory of Open Access Journals (Sweden)

    Yu. V. Ishkov

    2014-12-01

    Full Text Available 5,10,15,20-(2-methoxy-3-quinolinylporphyrine, which was a mixture of atropisomers, was obtained by condensation of 2-methoxyquinoline-3-carbaldehyde with pyrrole in propionic acid. Quaternization of nitrogen atoms of peripheric substituents in this compound lead to water soluble sterically hindered porphyrine.

  12. Synthesis and characterization of water-soluble carbon nanotubes ...

    Indian Academy of Sciences (India)

    Abstract. Carbon nanotubes (CNT) has been synthesized by pyrolysing mustard oil using an oil lamp. It was made water-soluble (wsCNT) through oxidative treatment by dilute nitric acid and was characterized by SEM, AFM, XRD, Raman and FTIR spec- troscopy. The synthesized wsCNT showed the presence of several ...

  13. Compositional analysis of water-soluble materials in switchgrass.

    Science.gov (United States)

    Chen, Shou-Feng; Mowery, Richard A; Sevcik, Richard S; Scarlata, Christopher J; Chambliss, C Kevin

    2010-03-24

    Any valuation of a potential feedstock for bioprocessing is inherently dependent upon detailed knowledge of its chemical composition. Accepted analytical procedures for compositional analysis of biomass water-soluble extracts currently enable near-quantitative mass closure on a dry weight basis. Techniques developed in conjunction with a previous analytical assessment of corn stover have been applied to assess the composition of water-soluble materials in four representative switchgrass samples. To date, analytical characterization of water-soluble material in switchgrass has resulted in >78% mass closures for all four switchgrass samples, three of which have a mass closure of >85%. Over 30 previously unknown constituents in aqueous extracts of switchgrass were identified and quantified using a variety of chromatographic techniques. Carbohydrates (primarily sucrose, glucose, and fructose) were found to be the predominant water-soluble components of switchgrass, accounting for 18-27% of the dry weight of extractives. Total glycans (monomeric and oligomeric sugars) contributed 25-32% to the dry weight of extractives. Additional constituents contributing to the mass balance for extractives included various alditols (2-3%), organic acids (10-13%), inorganic ions (11-13%), and a distribution of oligomers presumed to represent a diverse mixture of lignin-carbohydrate complexes (30-35%). Switchgrass results are compared with previous analyses of corn stover extracts and presented in the context of their potential impact on biomass processing, feedstock storage, and future analyses of feedstock composition.

  14. Short Communication Relationships between the water solubility of ...

    African Journals Online (AJOL)

    132. Short Communication. Relationships between the water solubility of roughage dry matter and certain chemical characteristics. J.W. Cilliers- and H.J. Cilliers. North West Agricultural Development lnstitute, Private. Bag X804, Potchefstroom, 2520 Republic of South Africa. Received 17 May 1995; accepted 8 August 1995.

  15. Site-specific in situ growth of an interferon-polymer conjugate that outperforms PEGASYS in cancer therapy.

    Science.gov (United States)

    Hu, Jin; Wang, Guilin; Zhao, Wenguo; Liu, Xinyu; Zhang, Libin; Gao, Weiping

    2016-07-01

    Conjugating poly(ethylene glycol) (PEG), PEGylation, to therapeutic proteins is widely used as a means to improve their pharmacokinetics and therapeutic potential. One prime example is PEGylated interferon-alpha (PEGASYS). However, PEGylation usually leads to a heterogeneous mixture of positional isomers with reduced bioactivity and low yield. Herein, we report site-specific in situ growth (SIG) of a PEG-like polymer, poly(oligo(ethylene glycol) methyl ether methacrylate) (POEGMA), from the C-terminus of interferon-alpha to form a site-specific (C-terminal) and stoichiometric (1:1) POEGMA conjugate of interferon-alpha in high yield. The POEGMA conjugate showed significantly improved pharmacokinetics, tumor accumulation and anticancer efficacy as compared to interferon-alpha. Notably, the POEGMA conjugate possessed a 7.2-fold higher in vitro antiproliferative bioactivity than PEGASYS. More importantly, in a murine cancer model, the POEGMA conjugate completely inhibited tumor growth and eradicated tumors of 75% mice without appreciable systemic toxicity, whereas at the same dose, no mice treated with PEGASYS survived for over 58 days. The outperformance of a site-specific POEGMA conjugate prepared by SIG over PEGASYS that is the current gold standard for interferon-alpha delivery suggests that SIG is of interest for the development of next-generation protein therapeutics. Copyright © 2016 Elsevier Ltd. All rights reserved.

  16. Synthesis of polymeric derivatives of isoniazid: characterization and in vitro release from a water-soluble adduct with polysuccinimide.

    Science.gov (United States)

    Giammona, G; Giannola, L I; Carlisi, B

    1989-04-01

    Coupling of isoniazid with polysuccinimide afforded a water-insoluble polymeric pro-drug; by reaction with ethanolamine it was chemically transformed in a water-soluble adduct. The in vitro release of isoniazid from the drug-polymer adduct was studied by using an artificial stomach wall lipid membrane. The transfer rate constant from simulated gastric juice to simulated plasma was defined and compared with that of an equivalent dose of pure drug.

  17. 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

  18. Ring Walking/Oxidative Addition Reactions for the Controlled Synthesis of Conjugated Polymers

    Energy Technology Data Exchange (ETDEWEB)

    Bazan, Guillermo C

    2012-04-03

    Power conversion efficiencies of plastic solar cells depend strongly on the molecular weight characteristics of the semiconducting polymers used for their fabrication. The synthesis of these materials typically relies on transition metal mediated catalytic reactions. In many instances, the ideal structures cannot be attained because of deficiencies in these reactions, particularly when it comes to being able to achieve high number average molecular weights and narrow molecular weight distributions. Another important conjugated polymer structure of interest is one in which a single functional group is attached at the end group of the chain. Such systems would be ideal for modifying surface properties at interfaces and for labeling biomolecular probes used in fluorescent biosensors. To respond to the challenges above, our efforts have centered on the design of homogenous transition metal complexes that are easy to prepare and effective in carrying out living, or quasi-living, condensative chain polymerization reactions. The key mechanistic challenge for the success of this reaction is to force the insertion of one monomer unit at a time via a process that involves migration of the transition metal-containing fragment to one terminus of the polymer chain. Chain growth characteristics are therefore favored when the metal does not dissociate from the newly formed reductive elimination product. We have proposed that dissociation is disfavored by the formation of a -complex, in which the metal can sample various locations of the electronically delocalized framework, a process that we term ring-walking , and find the functionality where oxidative addition takes place. Success has been achieved in the nickel-mediated cross coupling reaction of Grignard reagents with aromatic halides by using bromo[1,2-bis(diphenylphosphino)ethane]phenylnickel. This reagent can yield poly(thiophene)s (one of the most widely used type of polymer in plastic solar cells) with excellent

  19. The effects of vibronic coupling on the photophysics of pi-conjugated oligomers and polymers

    Science.gov (United States)

    Yamagata, Hajime

    A theoretical model describing photophysics of pi-conjugated aggregates, such as molecular crystals and polymer thin films, is developed. A Holstein-like Hamiltonian expressed with a multi-particle basis set is used to evaluate absorption and photoluminescence (PL) spectra. An analysis with line strength ratio proves to be a powerful diagnostic tool to obtain additional spectral signatures with which to distinguish H- vs. J-aggregation. For the H-aggregates absorption peak ratio, A 0-0/A 0-1, diminishes as the excitonic coupling increases. Also the PL peak ratio, I 0-0/I 0-1, is zero at T=0K with no disorder and the value increases as temperature and disorder increase. By contrast the J-aggregates show the opposite trends. Furthermore we will show the PL peak ratio provides a direct measurement of the exciton coherence length for a linear J-aggregate and could be expressed as I0-0/I 0-1 = Ncoh/gamma2. We will also show that it is inversely proportional to square root of temperature (T-1/2). Applying our theory to the herringbone style oligoacene molecular crystals, we show the lowest singlet exciton states are highly influenced by charge transfer (CT) states and the well known energetic gap in two polarized absorption spectra, so called Davydov Splitting (DS), is a product of the interaction. We have successfully reproduced the DS for all three oligoacenes without any free parameters. Inspired by the CT contribution in oligoacene crystals, we further develop Wannier-Mott exciton model and apply to disorder-free polydiacetylene (PDA) quantum wires, which have been shown to be extremely emissive. We will show the quantum wire is a J-aggregate and we once again derive the peak ratio and the coherence size relation, I0-0/I 0-1 = kappaNcoh/gamma 2, where kappa is a prefactor close to unity. Typical photophysical properties of polymer pi-stacks such as those occurring in P3HT films are well explained by the simple linear H-aggregate model. However several groups have

  20. Mechanistic studies of the structure-photostability relationship of organic conjugated polymers

    Science.gov (United States)

    Sanow, Logan Paul

    Organic Conjugated polymers (CPs) are a subject of intense research for their application in organic photovoltaics (OPVs), organic light emitting diodes (OLEDs), solid-state dye lasing, biological imaging and sensing, chemical sensing and remote sensing. CPs are key materials in the quest for more sustainable forms of renewable energy, making electronics more versatile and light weight, and increasing the functionality of everyday materials. For these applications and others that use CPs as the photoactive material, one of their main drawbacks is their susceptibility to photodegradation. Photodegradation occurs when the material is exposed to light leading to irreversible changes in the materials, most often resulting from photoxidation. These irreversible changes cause loss of mechanical, electronic and photophysical characteristics. For practical applications of CP devices, lifetime is as important as device efficiency. The following research is focused on studying the photodegradation mechanisms in various CPs to better understand the relationship between structure and stability, which may lead to the design of CPs which are more intrinsically photostable. To study how dependent photostability is on a polymer's chemical structure and frontier orbital energies, two series of CPs were studied. The first series contained two dicyano-substituted polyphenylenevinylene polymers with different side chains: poly(2,5-dioctyl-1,4-phenylene-1,2-dicyanovinylene) (C8-diCN-PPV) and poly(2,5-bis(decyloxy)-1,4-phenylene-1,2-dicyanovinylene) (RO-diCN-PPV). The second series included a well-known polymer, poly(3-hexylthiophene) (P3HT), and a newly synthesized CP, Poly(3,5-didodecyl-cyclopenta[2,1-b;3,4-b']dithiophen-4-one) (C6-CPDTO). The photodegradation mechanisms were studied through a combination of UV-Vis, PL, FTIR and NMR spectroscopy as well as gel permeation chromatography. There are two main degradation mechanisms that lead to photodegradation of CPs, the radical

  1. Photo-processing P3HT conjugated polymers, in solution: A new route towards ordered polymeric structures.

    Science.gov (United States)

    Barbosa Neto, Newton; Dutra, Marcia; Araujo, Paulo; Sampaio, Renato

    Solution aggregated thin films of conjugated polymers have demonstrated to be promising materials for many applications, e.g., solar cells and field-effect transistors. There are many standard methods to generate aggregates in polymeric solution, which includes poor solvent addiction and solution temperature manipulation. Here, we demonstrate a new approach to induce aggregate formation on solution of P3HT polymer. Under light excitation with 355 nm or 532 nm pulsed laser the polymer exhibit significant changes on its UV-Vis spectrum which are most known in the literature as the formation of H-J aggregates and additional new bands associated with polaron formation. Such changes in the amorphous phase of the polymers are seen in specific conditions of solvent combinations. We show also the dependency on the excitation laser power which can be identified as a threshold to ignite the formation of the new structure. We are grateful to CNPq and CAPES for financial support.

  2. Molding P3HT conjugated polymer in fibers by solvent-annealing-induced nanowetting in porous template

    Science.gov (United States)

    Cidade, Fernando N.; de Deus, Jeferson F.; Macedo, Andreia G.

    2015-07-01

    In this work, poly[3-hexyl-thiophene] (P3HT) polymer was assembled in fibers-like structures using a post-deposition treatment denoted as solvent-annealing-induced nanowetting in templates (SAINT). In this procedure, the as cast P3HT films deposited onto glass (or flexible) substrate are placed in contact with a porous template for instance, anodic alumina oxide (AAO), and then exposed to an atmosphere saturated with vapors of an organic solvent. This will induce a partial dissolution of the polymer and infiltration into the porous. After this, the template can be selectively removed and large areas containing tubular or fibers structures of polymer can be achieved. This is a simple procedure to produce fibers of conjugated polymer in films with enhanced optical and electrical properties that allows their application in optoelectronic devices.

  3. 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 (Tm) 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 (Ta) 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 Tm in these systems, as the number of ONA-star polymer arms increase, the assembly temperature Ta 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.

  4. Fluorescent π-conjugated polymer dots versus self-assembled small-molecule nanoparticles: what's the difference?

    Science.gov (United States)

    Fischer, Irén; Kaeser, Adrien; Peters-Gumbs, Mauraline A M; Schenning, Albertus P H J

    2013-08-12

    Fluorescent nanoparticles based on π-conjugated small molecules and polymers are two different classes of π-conjugated systems that have attracted much interest. To date, both emerging classes have only been studied separately and showed no clear differences in their properties. Herein these nanoparticles are compared on the basis of a fluorene co-polymer and its corresponding small molecule. Both systems formed nanoparticles with the same diameter, whereas the fluorescence properties clearly differed. In case of the polymer the fluorescence diminished, whereas for the small molecules the fluorescence increased. In addition, the capability of encapsulation and release of a hydrophobic dye from the fluorescent nanoparticles was studied. For the polymer system, encapsulation was highly efficient and no release was observed, whereas for the small molecule system encapsulation was less efficient and release of the dye was observed. These studies show a clear difference between small molecules and polymers which has important implications for the design of fluorescent nanoparticles. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  5. 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.

  6. Photo- and pH-tunable multicolor fluorescent nanoparticle-based spiropyran- and BODIPY-conjugated polymer with graphene oxide.

    Science.gov (United States)

    Sharker, Shazid Md; Jeong, Chan Jin; Kim, Sung Min; Lee, Jung-Eun; Jeong, Ji Hoon; In, Insik; Lee, Haeshin; Park, Sung Young

    2014-10-01

    We report a stimuli-responsive fluorescent nanomaterial, based on graphene oxide coupled with a polymer conjugated with photochromic spiropyran (SP) dye and hydrophobic boron dipyrromethane (BODIPY) dye, for application in triggered target multicolor bioimaging. Graphene oxide (GO) was reduced by catechol-conjugated polymers under mildly alkaline conditions, which enabled to formation of functionalized multicolor graphene nanoparticles that can be induced by irradiation with UV light and by changing the pH from acidic to neutral. Investigation of these nanoparticles by using AFM, fluorescence emission, and in vitro cell and in vivo imaging revealed that they show different tunable colors in bioimaging applications and, more specifically, in cancer-cell detection. The stability, biocompatibility, and quenching efficacy of this nanocomposite open a different perspective for cell imaging in different independent colors, sequentially and simultaneously. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. 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.

  8. Ultrafine Silver Nanoparticles Supported on a Conjugated Microporous Polymer as High-Performance Nanocatalysts for Nitrophenol Reduction.

    Science.gov (United States)

    Cao, Hai-Lei; Huang, Hai-Bo; Chen, Zhi; Karadeniz, Bahar; Lü, Jian; Cao, Rong

    2017-02-15

    A conjugated microporous polymer (CMP) material was designed with pore function of cyano and pyridyl groups that act as potential binding sites for Ag+ ion capture. Ultrafine silver nanoparticles (less than 5 nm) were successfully supported on the predesigned CMP material to afford Ag0@CMP composite materials by means of a simple liquid impregnation and light-induced reduction method. Spherical Ag0 nanoparticles with a statistical mean diameter of ca. 3.9 nm were observed and characterized by scanning electron microscopy and transmission electron microscopy. The Ag0@CMP composite materials were consequently exploited as high-performance nanocatalysts for the reduction of nitrophenols, a family of priority pollutants, at various temperatures and ambient pressure. Moreover, the composite nanocatalysts feature convenient recovery and excellent reusability. This work presents an efficient platform to achieve ultrafine metal nanoparticles immobilized on porous supports with predominant catalytic properties by virtue of the structural design and spatial confinement effect available for conjugated microporous polymers.

  9. Single-crystal-conjugated polymers with extremely high electron sensitivity through template-assisted in situ polymerization.

    Science.gov (United States)

    Xue, Mianqi; Wang, Yue; Wang, Xiaowei; Huang, Xiaochun; Ji, Junhui

    2015-10-21

    Single-crystal-conjugated polymer (SCCP) arrays are prepared successfully via a simple method, which is a combination of the contact thermochemical reaction and solvent-free in situ polymerization. The dramatic X-ray diffraction and selective-area electron diffraction results show the high crystallinity of the SCCP arrays. These SCCP arrays display unique physical properties and show great potential in flexible electronics. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. Simultaneous enhancement of open-circuit voltage, short-circuit current density, and fill factor in polymer solar cells

    Energy Technology Data Exchange (ETDEWEB)

    He, Zhicai; Zhong, Chengmei; Wu, Hongbin; Su, Shijian; Cao, Yong [Institute of Polymer Optoelectronic Materials and Devices, State Key Laboratory of Luminescent Materials and Devices, South China University of Technology, Guangzhou 510640 (China); Huang, Xun; Chen, Liwei [Suzhou Institute of Nano-Tech and Nano-Bionics, Chinese Academy of Sciences, 398 Ruoshui Road, Suzhou Industrial Park, Suzhou 215123 (China); Wong, Wai-Yeung [Institute of Molecular Functional Materials (Areas of Excellence Scheme, University Grants Committee, Hong Kong) and Department of Chemistry and Centre for Advanced Luminescence Materials, Hong Kong Baptist University, Waterloo Road, Hong Kong (China)

    2011-10-25

    Simultaneous enhancement of open-circuit voltage, short-circuit current density, and fill factor in highly efficient polymer solar cells by incorporating an alcohol/water-soluble conjugated polymer as cathode interlayer is domonstrated. When combined with a low-bandgap polymer PTB7 as the electron donor material, the power efficiency of the devices is improved to certified 8.370%. Due to drastic improvement in efficiency and easy utilization, this method opens new opportunities for PSCs from various material systems to improve towards 10% efficiency. (Copyright copyright 2011 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  11. Fabrication and capacitive characteristics of conjugated polymer composite p-polyaniline/n-WO{sub 3} heterojunction

    Energy Technology Data Exchange (ETDEWEB)

    Amaechi, C.I.; Asogwa, P.U.; Ekwealor, A.B.C. [University of Nigeria, Department of Physics and Astronomy, Nsukka, Enugu State (Nigeria); Osuji, R.U.; Ezema, F.I. [University of Nigeria, Department of Physics and Astronomy, Nsukka, Enugu State (Nigeria); iThemba LABS-National Research Foundation, Nanosciences African Network (NANOAFNET), Somerset West, Western Cape Province (South Africa); University of South Africa (UNISA), UNESCO-UNISA Africa Chair in Nanosciences/Nanotechnology, College of Graduate Studies, Pretoria (South Africa); Maaza, M. [iThemba LABS-National Research Foundation, Nanosciences African Network (NANOAFNET), Somerset West, Western Cape Province (South Africa); University of South Africa (UNISA), UNESCO-UNISA Africa Chair in Nanosciences/Nanotechnology, College of Graduate Studies, Pretoria (South Africa)

    2014-11-15

    A nanocrystalline and porous p-polyaniline/n-WO{sub 3} dissimilar heterojunction at ambient temperature is reported. The high-quality and well-reproducible conjugated polymer composite films have been fabricated by oxidative polymerization of anilinium ion on predeposited WO{sub 3} thin film by chemical bath deposition followed by thermal annealing at 573 K for 1 h. Atomic force microscopy (AFM) analyses reveal a homogenous but irregular cluster of faceted spherically shaped grains with pores. The scanning electron microscopy confirms the porous network of grains, which is in good agreement with the AFM result. The optical absorption analysis of polyaniline/WO{sub 3} hybrid films showed that direct optical transition exist in the photon energy range 3.50-4.00 eV with bandgap of 3.70 eV. The refractive index developed peak at 445 nm in the dispersion region while the high-frequency dielectric constant, ε {sub ∞}, and the carrier concentration to effective mass ratio, N/m{sup *}, was found to be 1.58 and 1.10 x 10{sup 39} cm{sup -3}, respectively. The temperature dependence of electrical resistivity of the deposited films follows the semiconductor behavior while the C-V characteristics (Mott-Schottky plots) show that the flat band potential was -791 and 830 meV/SCE for WO{sub 3} and polyaniline. (orig.)

  12. Multi-colored fibers by self-assembly of DNA, histone proteins, and cationic conjugated polymers.

    Science.gov (United States)

    Wang, Fengyan; Liu, Zhang; Wang, Bing; Feng, Liheng; Liu, Libing; Lv, Fengting; Wang, Yilin; Wang, Shu

    2014-01-07

    The development of biomolecular fiber materials with imaging ability has become more and more useful for biological applications. In this work, cationic conjugated polymers (CCPs) were used to construct inherent fluorescent microfibers with natural biological macromolecules (DNA and histone proteins) through the interfacial polyelectrolyte complexation (IPC) procedure. Isothermal titration microcalorimetry results show that the driving forces for fiber formation are electrostatic and hydrophobic interactions, as well as the release of counterions and bound water molecules. Color-encoded IPC fibers were also obtained based on the co-assembly of DNA, histone proteins, and blue-, green-, or red- (RGB-) emissive CCPs by tuning the fluorescence resonance energy-transfer among the CCPs at a single excitation wavelength. The fibers could encapsulate GFP-coded Escherichia coli BL21, and the expression of GFP proteins was successfully regulated by the external environment of the fibers. These multi-colored fibers show a great potential in biomedical applications, such as biosensor, delivery, and release of biological molecules and tissue engineering. Copyright © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  13. Manipulation of Chain Conformation for Optimum Charge-Transport Pathways in Conjugated Polymers.

    Science.gov (United States)

    Jeon, Seolhee; Lee, Jung Hun; Park, Jai Il; Jo, Bonghyun; Whang, Dong Ryeol; Ahn, Tae Kyu; Park, Hui Joon; Kim, Sung Dong; Lee, Wi Hyoung; Kim, Bong-Gi

    2017-07-12

    A pair of different diketopyrrolopyrrole-based conjugated polymers (CPs) were designed and synthesized to investigate the effect of chain conformation on their molecular assembly. Conformation management was achieved by the incorporation of different linkers during polymerization. Through the use of computational calculations and UV-vis absorption measurements, the resulting CPs (PDPP-T and PDPP-BT) were found to exhibit partly modulated chain geometry. Grazing incident X-ray diffraction experiments with a two-dimensional detector revealed that PDPP-T having a planar chain conformation exhibited an edge-on type molecular arrangement, which evolved to a face-on type chain assembly when the planar geometry was altered to a slightly twisted one as in PDPP-BT. In addition, it was verified that the directional electric carrier mobility of CPs was critically distinguished by the distinctive chain arrangement in spite of their similar chemical structure. Concentration-dependent absorption measurements could provide an improved understanding of the assembly mechanism of CP chains: the planar conformation of PDPP-T facilitates the formation of preassembled chains in a concentrated solution and further directs the edge-on stacking, while the twisted dihedral angle along the benzothiophene in PDPP-BT prevents chain assembly, resulting in the face-on stacking. Because CP chain conformation is inevitably connected with the generation of preassembled chains, manipulating CP geometry could be an efficient tool for extracting an optimum chain assembly that is connected with the principal charge-transport pathway in CPs.

  14. Controlling ion motion in polymer light-emitting diodes containing conjugated polyelectrolyte electron injection layers.

    Science.gov (United States)

    Garcia, Andres; Bakus, Ronald C; Zalar, Peter; Hoven, Corey V; Brzezinski, Jacek Z; Nguyen, Thuc-Quyen

    2011-03-02

    The properties and function of an anionic conjugated polyelectrolyte (CPE)-containing ion-conducting polyethylene oxide pendant (PF(PEO)CO(2)Na) as electron injection layers (EILs) in polymer light-emitting diodes (PLEDs) are investigated. A primary goal was to design a CPE structure that would enable acceleration of the device temporal response through facilitation of ion motion. Pristine PLEDs containing PF(PEO)CO(2)Na exhibit luminance response times on the order of tenths of seconds. This delay is attributed to the formation of ordered structures within the CPE film, as observed by atomic force microscopy. Complementary evidence is provided by electron transport measurements. The ordered structures are believed to slow ion migration within the CPE EIL and hence result in a longer temporal response time. It is possible to accelerate the response by a combination of thermal and voltage treatments that "lock" ions within the interfaces adjacent to PF(PEO)CO(2)Na. PLED devices with luminance response times of microseconds, a 10(5) fold enhancement, can therefore be achieved. Faster luminance response time opens up the application of PLEDs with CPE layers in display technologies.

  15. Wafer-Scale Ultrathin Two-Dimensional Conjugated Microporous Polymers: Preparation and Application in Heterostructure Devices.

    Science.gov (United States)

    Liu, Zhengdong; Song, Mengya; Ju, Shang; Huang, Xiao; Wang, Xiangjing; Shi, Xiaotong; Zhu, Ya; Wang, Zhan; Chen, Jie; Li, Hai; Cheng, Yingchun; Xie, Linghai; Liu, Juqing; Huang, Wei

    2018-01-31

    In this work, we report a universal surface-assisted oxidative polymerization strategy for wafer-scale fabrication of ultrathin two-dimensional conjugated microporous polymers (2D CMPs) on arbitrary substrates under ambient conditions. Three kinds of 2D CMPs with average thickness of 1.5-3.6 nm were prepared on SiO2/Si substrates by using carbazole based monomers. Moreover, 2D CMPs can be grown on reduced graphene oxide (rGO) substrate to construct large-area 2D CMP/rGO heterostructure. As a proof-of-concept demonstration, an organic vertical field-effect transistor based on 2D CMP/rGO heterostructures was fabricated, which exhibited typical p-type behavior with high reproducibility and on/off current ratio. Most importantly, the direct growth of large-area 2D CMPs on arbitrary substrates is compatible with the conventional processes in the semiconductor industry, and therefore is expected to expedite the development of 2D CMPs as building blocks for construction of practical electronic devices.

  16. 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

    2018-01-15

    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 m2 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 H2 SO4 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.

  17. Core shell hybrids based on noble metal nanoparticles and conjugated polymers: synthesis and characterization

    Directory of Open Access Journals (Sweden)

    Battocchio Chiara

    2011-01-01

    Full Text Available Abstract Noble metal nanoparticles of different sizes and shapes combined with conjugated functional polymers give rise to advanced core shell hybrids with interesting physical characteristics and potential applications in sensors or cancer therapy. In this paper, a versatile and facile synthesis of core shell systems based on noble metal nanoparticles (AuNPs, AgNPs, PtNPs, coated by copolymers belonging to the class of substituted polyacetylenes has been developed. The polymeric shells containing functionalities such as phenyl, ammonium, or thiol pending groups have been chosen in order to tune hydrophilic and hydrophobic properties and solubility of the target core shell hybrids. The Au, Ag, or Pt nanoparticles coated by poly(dimethylpropargylamonium chloride, or poly(phenylacetylene-co-allylmercaptan. The chemical structure of polymeric shell, size and size distribution and optical properties of hybrids have been assessed. The mean diameter of the metal core has been measured (about 10-30 nm with polymeric shell of about 2 nm.

  18. Conjugated polymers nanostructured as smart interfaces for controlling the catalytic properties of enzymes.

    Science.gov (United States)

    Barbosa, Camila Gouveia; Caseli, Luciano; Péres, Laura Oliveira

    2016-08-15

    The search for new molecular architectures to improve the efficiency of enzymes entrapped in ultrathin films is useful to enhance the effectiveness of biosensors. In this present work, conjugated polymers, based on thiophene and fluorine, were investigated to verify their suitability as matrices for the immobilization of urease. The copolymer poly[(9,9-dioctylfluorene)-co-thiophene], PDOF-co-Th was spread on the air-water interface forming stable Langmuir monolayers as determined by surface pressure-area isotherms, polarization-modulation reflection-absorption infrared spectroscopy (PM-IRRAS), and Brewster angle microscopy (BAM). Urease was incorporated in the floating monolayers being further transferred to solid supports as mixed Langmuir-Blodgett (LB) films. These films were then characterized with transfer ratio, fluorescence spectroscopy, PM-IRRAS and atomic force microscopy, confirming the co-transfer of the enzyme as well as its structuring in β-sheets. The catalytic activity was detected for urease, with a lower reaction rate than that encountered for the homogeneous environment. This was attributed to conformational constraints imposed to the biomacromolecule entrapped in the polymeric matrix. Copyright © 2016 Elsevier Inc. All rights reserved.

  19. Au nanorods modulated NIR fluorescence and singlet oxygen generation of water soluble dendritic zinc phthalocyanine.

    Science.gov (United States)

    Zhou, Xuefei; He, Xiaohong; Wei, Shiliang; Jia, Kun; Liu, Xiaobo

    2016-11-15

    A novel cyano-terminated zinc phthalocyanine (ZnPc-CN) exhibiting visible near infrared (vis-NIR) emitting around 690nm in N,N-dimethylformamide (DMF) solvent has been synthesized. Furthermore, the peripheral cyano groups of newly synthesized zinc phthalocyanine were hydrolyzed in strong basic solution, leading to water soluble carboxylated zinc phthalocyanine (ZnPc-COOH) with completely quenched fluorescence in aqueous solution. Interestingly, we found that the NIR fluorescence of aqueous ZnPc-COOH was dramatically recovered in the presence of gold nanorods (Au NR), which was due to the alternation of ZnPc-COOH molecules self-assembling via electrostatic interaction between cetyltrimethylammonium bromide (CTAB) on the surface of Au NR and peripheral carboxyl of ZnPc-COOH. In addition, ZnPc-COOH/Au NR conjugates demonstrated an improved singlet oxygen generation, which could be served as potential bioimaging probe and photosensitizer for photodynamic therapy. Copyright © 2016 Elsevier Inc. All rights reserved.

  20. 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.

  1. Tuning backbones and side-chains of cationic conjugated polymers for optical signal amplification of fluorescent DNA detection.

    Science.gov (United States)

    Huang, Yan-Qin; Liu, Xing-Fen; Fan, Qu-Li; Wang, Lihua; Song, Shiping; Wang, Lian-Hui; Fan, Chunhai; Huang, Wei

    2009-06-15

    Three cationic conjugated polymers (CCPs) exhibiting different backbone geometries and charge densities were used to investigate how their conjugated backbone and side chain properties, together with the transitions of DNA amphiphilic properties, interplay in the CCP/DNA-C* (DNA-C*: fluorophore-labeled DNA) complexes to influence the optical signal amplification of fluorescent DNA detection based on Förster resonance energy transfer (FRET). By examining the FRET efficiencies to dsDNA-C* (dsDNA: double-stranded DNA) and ssDNA-C* (ssDNA: single-stranded DNA) for each CCP, twisted conjugated backbones and higher charge densities were proved to facilitate electrostatic attraction in CCP/dsDNA-C* complexes, and induced improved sensitivity to DNA hybridization. Especially, by using the CCP with twisted conjugated backbone and the highest charge density, a more than 7-fold higher efficiency of FRET to dsDNA-C* was found than to ssDNA-C*, indicating a high signal amplification for discriminating between dsDNA and ssDNA. By contrast, linear conjugated backbones and lower charge density were demonstrated to favor hydrophobic interactions in CCP/ssDNA-C* complexes. These findings provided guidelines for the design of novel sensitive CCP, which can be useful to recognize many other important DNA activities involving transitions of DNA amphiphilic properties like DNA hybridization, such as specific DNA binding with ions, some secondary or tertiary structural changes of DNA, and so forth.

  2. Cytotoxicity evaluation and antimicrobial studies of starch capped water soluble copper nanoparticles

    Energy Technology Data Exchange (ETDEWEB)

    Valodkar, Mayur; Rathore, Puran Singh [Department of Chemistry, Faculty of Science, The Maharaja Sayajirao University of Baroda, Vadodara 390002, Gujarat (India); Jadeja, Ravirajsinh N.; Thounaojam, Menaka; Devkar, Ranjitsinh V. [Department of Zoology, Faculty of Science, The Maharaja Sayajirao University of Baroda, Vadodara 390002, Gujarat (India); Thakore, Sonal, E-mail: chemistry2797@yahoo.com [Department of Chemistry, Faculty of Science, The Maharaja Sayajirao University of Baroda, Vadodara 390002, Gujarat (India)

    2012-01-30

    Highlights: Black-Right-Pointing-Pointer Bactericidal action of water soluble starch copper nanoconjugate was investigated. Black-Right-Pointing-Pointer Mode of action comparable to ampicillin and MIC as low as 1.6 {mu}g/ml. Black-Right-Pointing-Pointer The SCuNPs were non-toxic to mouse embryonic fibroblasts. Black-Right-Pointing-Pointer Cell viability was higher than uncapped CuNPs and cupric ions. Black-Right-Pointing-Pointer Promising biomedical applications due to high therapeutic index. - Abstract: Water soluble monodisperse copper nanoparticles of about 10 nm diameter were prepared by microwave irradiation using starch as green capping agent. The resulting Cu-starch conjugate were characterized by FTIR and energy dispersive X-ray analysis (EDX). The study confirmed the presence of copper embedded in polysaccharide matrix. The aqueous solution of starch capped copper nanoparticles (SCuNPs) exhibited excellent bactericidal action against both gram negative and gram positive bacteria. The in vitro cytotoxicity evaluation of the nanoparticles was carried out using mouse embryonic fibroblast (3T3L1) cells by MTT cell viability assay, extracellular lactate dehydrogenase (LDH) release and dark field microscopy imaging. The capped nanoparticles exhibited cytotoxicity at much higher concentration compared to cupric ions. Minimum bactericidal concentration (MBC) of SCuNPs was well below the in vitro cytotoxic concentration. Statistical analysis demonstrated p < 0.05 for significant results and p > 0.05 for non-significant ones as compared to untreated cells. The non-cytotoxic green Cu-starch conjugate offers a rational approach towards antimicrobial application and for integration to biomedical devices.

  3. Size-Controlled Water-Soluble Ag Nanoparticles

    OpenAIRE

    Dominguez-Vera, J. M.; Galvez, N.; Sanchez, P; A. J. Mota; Trasobares Llorente, Susana; Hernandez, J.C.; Calvino Gámez, José Juan

    2007-01-01

    Ag nanoparticles of two different sizes (1 and 4 nm) were prepared within an apoferritin cavity by using an Ag+-loaded apoferritin as a nanoconfined environment for their construction. The initial amount of Ag' ions injected in the apoferritin cavity dictates the size of the final Ag particles. The protein shell prevents bulk aggregation of the metal particles, which renders them water soluble and extremely stable.

  4. Synthesis of Water-Soluble Deep-Cavity Cavitands.

    Science.gov (United States)

    Hillyer, Matthew B; Gibb, Corinne L D; Sokkalingam, Punidha; Jordan, Jacobs H; Ioup, Sarah E; Gibb, Bruce C

    2016-08-19

    An efficient, four-step synthesis of a range of water-soluble, deep-cavity cavitands is presented. Key to this approach are octahalide derivatives (4, X = Cl or Br) that allow a range of water-solubilizing groups to be added to the outer surface of the core host structure. In many cases, the conversion of the starting dodecol (1) resorcinarene to the different cavitands avoids any chromatographic procedures.

  5. Hydrocarbon molar water solubility predicts NMDA vs. GABAA receptor modulation.

    Science.gov (United States)

    Brosnan, Robert J; Pham, Trung L

    2014-11-19

    Many anesthetics modulate 3-transmembrane (such as NMDA) and 4-transmembrane (such as GABAA) receptors. Clinical and experimental anesthetics exhibiting receptor family specificity often have low water solubility. We hypothesized that the molar water solubility of a hydrocarbon could be used to predict receptor modulation in vitro. GABAA (α1β2γ2s) or NMDA (NR1/NR2A) receptors were expressed in oocytes and studied using standard two-electrode voltage clamp techniques. Hydrocarbons from 14 different organic functional groups were studied at saturated concentrations, and compounds within each group differed only by the carbon number at the ω-position or within a saturated ring. An effect on GABAA or NMDA receptors was defined as a 10% or greater reversible current change from baseline that was statistically different from zero. Hydrocarbon moieties potentiated GABAA and inhibited NMDA receptor currents with at least some members from each functional group modulating both receptor types. A water solubility cut-off for NMDA receptors occurred at 1.1 mM with a 95% CI = 0.45 to 2.8 mM. NMDA receptor cut-off effects were not well correlated with hydrocarbon chain length or molecular volume. No cut-off was observed for GABAA receptors within the solubility range of hydrocarbons studied. Hydrocarbon modulation of NMDA receptor function exhibits a molar water solubility cut-off. Differences between unrelated receptor cut-off values suggest that the number, affinity, or efficacy of protein-hydrocarbon interactions at these sites likely differ.

  6. Top-down prepared silicon nanocrystals and a conjugated polymer-based bulk heterojunction: Optoelectronic and photovoltaic applications

    Energy Technology Data Exchange (ETDEWEB)

    Svrcek, Vladimir, E-mail: vladimir.svrcek@aist.go.jp [Novel Silicon Material Team, Research Center for Photovoltaics, National Institute of Advanced Industrial Science and Technology (AIST), Central 2, Umezono 1-1-1, Tsukuba 305-8568 (Japan); Fujiwara, Hiroyuki; Kondo, Michio [Novel Silicon Material Team, Research Center for Photovoltaics, National Institute of Advanced Industrial Science and Technology (AIST), Central 2, Umezono 1-1-1, Tsukuba 305-8568 (Japan)

    2009-12-15

    Blends consisting of doped silicon nanocrystals (Si-ncs) and two conjugated polymers (poly(3-hexylthiophene) (P3HT) and poly(methoxy ethylexyloxy phenylenevinilene) (MEH PPV)) with improved photostability were fabricated. We show that a top-down approach by electrochemical etching is suitable for preparing doped (boron and phosphorus) freestanding and surfactant-free Si-ncs. The doping of Si-ncs was confirmed by low temperature photoluminescence and electron spin resonance analysis. It is demonstrated that such Si-ncs can be successfully used for the fabrication of room temperature photoluminescent and photosensitive blends. We argue that the luminescence and transport properties of the blends are controlled by the Si-ncs properties and could be assigned to quantum confinement of excitons in nanocrystalites with an energy band gap of {approx}2 eV. Furthermore, the blending of doped Si-ncs in both conjugated polymers led to the establishment of a bulk heterojunction between the Si-ncs and polymer. The difference in electron affinity and ionization potential between nanocrystals and polymer dissociated the excitons. Those blends showed increased carrier transport and photoconductivity under ambient conditions. It was found that introduction of less defective p-type doped Si-ncs significantly improved overall photostability of the blend. The Si-ncs non-toxicity and easy integration into well-established silicon technologies might bring considerable benefit for hybrid optoelectronic and photovoltaic device development.

  7. Highly sensitive detection of nitroaromatic explosives using an electrospun nanofibrous sensor based on a novel fluorescent conjugated polymer.

    Science.gov (United States)

    Long, Yuanyuan; Chen, Haibo; Wang, Huaming; Peng, Zhou; Yang, Yufei; Zhang, Guoqing; Li, Na; Liu, Feng; Pei, Jian

    2012-09-26

    An electrospun nanofibrous explosive sensor was first constructed based on a newly developed fluorescent conjugated polymer P containing heteroatom polycyclic units. Electrospinning by doping polymer P as a fluorescent probe in a polystyrene supporting matrix afforded a fluorescence nanofibrous film with unique porous structures, and effectively avoided the aggregation of polymer P. The novel explosive sensor exhibited stable fluorescence property, satisfactory reversibility with less than 5% loss of signal intensity after four quenching-regeneration cycles, and good reproducibility among three batches with a relative standard deviation of 2.8%. Such fabricated sensor also showed remarkable sensitivity toward a series of trace nitroaromatic explosive vapors, including picric acid (parts-per-trillion level) and 2,4,6-trinitrotoluene vapor (parts-per-billion level), as well as good selectivity with less than 10% response to typical interferents. Therefore, the present strategy extends the application of different kinds of conjugated polymers for the construction of optical chemosensors. Copyright © 2012 Elsevier B.V. All rights reserved.

  8. Preparation, properties and applications in cell imaging and ions detection of conjugated polymer nanoparticles with alcoxyl bonding fluorene core.

    Science.gov (United States)

    Feng, Liheng; Guo, Lixia; Wang, Xiaoju

    2017-01-15

    A novel conjugated polymer (PFP) comprised of fluorene, benzene and alcoxyl units was synthesized by a Suzuki coupling reaction between fluorene borate and dibromobenzene derivant. Due to its longer alcoxyl groups in the side chain, PFP polymer possesses good solubility in common organic solvents. Accordingly, conjugated polymer nanoparticles (CPNs) from PFP polymer were easily prepared by a re-precipitation method. A spherical structure of the CPNs with an average diameter of ~75nm was verified by dynamic light scattering (DLS) and scanning electron microscopy (SEM). The CPNs exhibit high photostability, good biocompatibility and low cytotoxicity. Based on these excellent properties, the CPNs as staining and labeling regents were used to cell imaging and located in the cytoplasm. Interestingly, the fluorescent probe based on CPNs displays high selectivity and sensitivity for Fe(III) in water because of the aggregation-induced fluorescence quenching action between CPNs and Fe(III). The contribution of the report lies in providing a new strategy for designing and developing CPNs-based probes, and applying in the interdisciplinary fields of chemistry, biology and material sciences. Copyright © 2016 Elsevier B.V. All rights reserved.

  9. Polyelectrolyte microcapsules for sustained delivery of water-soluble drugs

    Energy Technology Data Exchange (ETDEWEB)

    Anandhakumar, S.; Debapriya, M. [Department of Materials Engineering, Indian Institute of Science, Bangalore, 560012 (India); Nagaraja, V. [Department of Microbiology and Cell Biology, Indian Institute of Science, Bangalore, 560012 (India); Raichur, Ashok M., E-mail: amr@materials.iisc.ernet.in [Department of Materials Engineering, Indian Institute of Science, Bangalore, 560012 (India)

    2011-03-12

    Polyelectrolyte capsules composed of weak polyelectrolytes are introduced as a simple and efficient system for spontaneous encapsulation of low molecular weight water-soluble drugs. Polyelectrolyte capsules were prepared by layer-by-layer (LbL) assembling of weak polyelectrolytes, poly(allylamine hydrochloride) (PAH) and poly(methacrylic acid) (PMA) on polystyrene sulfonate (PSS) doped CaCO{sub 3} particles followed by core removal with ethylene-diaminetetraacetic acid (EDTA). The loading process was observed by confocal laser scanning microscopy (CLSM) using tetramethylrhodamineisothiocyanate labeled dextran (TRITC-dextran) as a fluorescent probe. The intensity of fluorescent probe inside the capsule decreased with increase in cross-linking time. Ciprofloxacin hydrochloride (a model water-soluble drug) was spontaneously deposited into PAH/PMA capsules and their morphological changes were investigated by scanning electron microscopy (SEM) and atomic force microscopy (AFM). The quantitative study of drug loading was also elucidated which showed that drug loading increased with initial drug concentration, but decreased with increase in pH. The loaded drug was released in a sustained manner for 6 h, which could be further extended by cross-linking the capsule wall. The released drug showed significant antibacterial activity against E. coli. These findings indicate that such capsules can be potential carriers for water-soluble drugs in sustained/controlled drug delivery applications.

  10. Below-Gap Excitation of π-Conjugated Polymer-Fullerene Blends: Implications for Bulk Organic Heterojunction Solar Cells

    Science.gov (United States)

    Drori, T.; Sheng, C.-X.; Ndobe, A.; Singh, S.; Holt, J.; Vardeny, Z. V.

    2008-07-01

    We used a variety of optoelectronic techniques such as broadband fs transient and cw photomodulation spectroscopies, electroabsorption, and short-circuit photocurrent in bulk heterojunctions organic solar cells for studying the photophysics in π-conjugated polymer-fullerene blends with below-gap excitation. In contrast to the traditional view, we found that below-gap excitation, which is incapable of generating intrachain excitons, nevertheless efficiently generates polarons on the polymer chains and fullerene molecules. The polaron action spectrum extends deep inside the gap as a result of a charge-transfer complex state formed between the polymer chain and fullerene molecule. With appropriate design engineering the long-lived polarons might be harvested in solar cell devices.

  11. Incorporation of titanate nanosheets to enhance mechanical properties of water-soluble polyamic acid

    Science.gov (United States)

    Harito, C.; Bavykin, Dmitry V.; Walsh, Frank C.

    2017-07-01

    Pyromeliticdianhydride (PMDA) and 4’,4’-oxydianiline (ODA) were used as monomers of polyimide. To synthesise a water soluble polyimide precursor (polyamic acid salt), triethylamine (TEA) was added to polyamic acid with a TEA/COOH mole ratio of 1:1. Titanate nanosheets were synthesised by solid-state reaction, ion-exchanged with acid, and exfoliated by TEA. Exfoliated titanate nanosheets were mixed with water soluble polyamic acid salt as reinforcing filler. Drop casting was deployed to synthesise polyamic acid/titanate nanosheet nanocomposite films. Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) were employed to study the morphology and dispersion of nanosheets in the colloidal dispersion and the solid film composite. Modulus and hardness of nanocomposites was provided by nanoindentation. Hardness increased by 90% with addition of 2% TiNS while modulus increased by 103% compared to pure polymer. This behaviour agrees well with Halpin-Tsai theoretical predictions up to 2 wt% filler loading; agglomeration occurs at higher concentrations.

  12. Preparation of Water-Soluble Homo and Copolymers of Bithiophene with 3,4-Ethylene Dioxythiophene and 3-Dodecylthiophene in Presence of Polystyrene Sulfonic Acid: Structure, Morphology, Thermal Stability

    Directory of Open Access Journals (Sweden)

    Bakhshali Massoumi

    2015-04-01

    Full Text Available Conductive polymers based on water-soluble polythiophenes were prepared. In this respect, alkylation reaction was carried out to synthesize the monomer 3-dodecylthiophene using 3-bromothiophene, bromododecane and magnesium. The monomer 2,2′-bithiophene was also prepared from 2-bromothiophene. Then, poly(2,2′-bithiophene, poly(3,4-ethylenedioxythiophene and poly(3-dodecylthiophene homopolymers were prepared at room temperature by successive chemical oxidation in the presence of polystyrene sulfonic acid and ammonium persulfate and water, as dopant, oxidant and solvent, respectively, under vigorous stirring. Under similar conditions, 2,2′-bithiophene copolymers with 3-dodecylthiophene and 3,4-ethylenedioxythiophene, copolymers with 3-dodecylthiophene were prepared at different molar ratios. To purify and dry the prepared polymers, dialysis tubs and freezing dry processes were applied. Structure of homo and copolymers were investigated by Fourier transform infrared (FTIR. Conjugated and planar structures of polymers were studied by Ultravoilet (UV-vis spectroscopy. The electrical conductivity of synthesized polymers was measured by four probe technique. The morphology and thermal stability of the products were studied using scanning electron microscopy (SEM, transmission electron microscopy (TEM and thermogravimetric analysis (TGA. Finally, solubility of homo and copolymers were tested in some organic solvents and water. Electro- activity of the prepared polymers was studied by cyclic voltammetry (CV on the glassy carbon (GC in LiClO4/CH3CN electrolyte solution and their electro-activity was confirmed. Electro-conductivity and electro-activity of homo and co polymers were low due topresence of polystyrene sulfonic acid which reduced the immobility of the polymers.

  13. Fabrication and Characterization of Conductive Conjugated Polymer-Coated Antheraea mylitta Silk Fibroin Fibers for Biomedical Applications.

    Science.gov (United States)

    Gh, Darshan; Kong, Dexu; Gautrot, Julien; Vootla, Shyam Kumar

    2017-07-01

    Conductive polymers are interesting materials for a number of biological and medical applications requiring electrical stimulation of cells or tissues. Highly conductive polymers (polypyrrole and polyaniline)/Antheraea mylitta silk fibroin coated fibers are fabricated successfully by in situ polymerization without any modification of the native silk fibroin. Coated fibers characterized by scanning electron microscopy confirm the silk fiber surface is covered by conductive polymers. Thermogravimetric analysis reveals preserved thermal stability of silk fiber after coating process. X-ray diffraction of degummed fiber diffraction peaks at around 2θ = 20.4 and 16.5 confirms the preservation of the β-sheet structure typical of degummed silk II fibers. This phenomenon implies that both polypyrrole and polyaniline chains form interactions with peptide linkages in degummed fiber macromolecules, without significantly disrupting protein assembly. Fourier transform infrared spectroscopy of coated fibers indicates hydrogen bonding and electrostatic interactions exist between silk fibroin macromolecules and conductive polymers. Resulting fibers display good conductive properties compared to corresponding conjugated polymers. In vitro analysis (live/dead assay) of the behavior of human immortalized keratinocytes (HaCaTs) on coated fibers demonstrates improved cell-adhesive properties and viability after polymers coating. Hence, polypyrrole- and polyaniline-coated A. mylitta silk fibers are suitable for application in cell culture and for tissue engineering, where electrical conduction properties are required. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. 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.

  15. Exciton Absorption Spectra by Linear Response Methods:Application to Conjugated Polymers

    Energy Technology Data Exchange (ETDEWEB)

    Mosquera, Martin A.; Jackson, Nicholas E.; Fauvell, Thomas J.; Kelley, Matthew S.; Chen, Lin X.; Schatz, George C.; Ratner, Mark A.

    2017-01-01

    The theoretical description of the timeevolution of excitons requires, as an initial step, the calculation of their spectra, which has been inaccessible to most users due to the high computational scaling of conventional algorithms and accuracy issues caused by common density functionals. Previously (J. Chem. Phys. 2016, 144, 204105), we developed a simple method that resolves these issues. Our scheme is based on a two-step calculation in which a linear-response TDDFT calculation is used to generate orbitals perturbed by the excitonic state, and then a second linear-response TDDFT calculation is used to determine the spectrum of excitations relative to the excitonic state. Herein, we apply this theory to study near-infrared absorption spectra of excitons in oligomers of the ubiquitous conjugated polymers poly(3-hexylthiophene) (P3HT), poly(2-methoxy-5-(2-ethylhexyloxy)-1,4-phenylenevinylene) (MEH-PPV), and poly(benzodithiophene-thieno[3,4-b]thiophene) (PTB7). For P3HT and MEH-PPV oligomers, the calculated intense absorption bands converge at the longest wavelengths for 10 monomer units, and show strong consistency with experimental measurements. The calculations confirm that the exciton spectral features in MEH-PPV overlap with those of the bipolaron formation. In addition, our calculations identify the exciton absorption bands in transient absorption spectra measured by our group for oligomers (1, 2, and 3 units) of PTB7. For all of the cases studied, we report the dominant orbital excitations contributing to the optically active excited state-excited state transitions, and suggest a simple rule to identify absorption peaks at the longest wavelengths. We suggest our methodology could be considered for further evelopments in theoretical transient spectroscopy to include nonadiabatic effects, coherences, and to describe the formation of species such as charge-transfer states and polaron pairs.

  16. Conjugated polymer nanoparticles for effective siRNA delivery to tobacco BY-2 protoplasts

    Directory of Open Access Journals (Sweden)

    Verchot Jeanmarie

    2010-12-01

    Full Text Available Abstract Background Post transcriptional gene silencing (PTGS is a mechanism harnessed by plant biologists to knock down gene expression. siRNAs contribute to PTGS that are synthesized from mRNAs or viral RNAs and function to guide cellular endoribonucleases to target mRNAs for degradation. Plant biologists have employed electroporation to deliver artificial siRNAs to plant protoplasts to study gene expression mechanisms at the single cell level. One drawback of electroporation is the extensive loss of viable protoplasts that occurs as a result of the transfection technology. Results We employed fluorescent conjugated polymer nanoparticles (CPNs to deliver siRNAs and knockdown a target gene in plant protoplasts. CPNs are non toxic to protoplasts, having little impact on viability over a 72 h period. Microscopy and flow cytometry reveal that CPNs can penetrate protoplasts within 2 h of delivery. Cellular uptake of CPNs/siRNA complexes were easily monitored using epifluorescence microscopy. We also demonstrate that CPNs can deliver siRNAs targeting specific genes in the cellulose biosynthesis pathway (NtCesA-1a and NtCesA-1b. Conclusions While prior work showed that NtCesA-1 is a factor involved in cell wall synthesis in whole plants, we demonstrate that the same gene plays an essential role in cell wall regeneration in isolated protoplasts. Cell wall biosynthesis is central to cell elongation, plant growth and development. The experiments presented here shows that NtCesA is also a factor in cell viability. We show that CPNs are valuable vehicles for delivering siRNAs to plant protoplasts to study vital cellular pathways at the single cell level.

  17. 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.

  18. Observation of a distinct surface molecular orientation in films of a high mobility conjugated polymer.

    Science.gov (United States)

    Schuettfort, Torben; Thomsen, Lars; McNeill, Christopher R

    2013-01-23

    The molecular orientation and microstructure of films of the high-mobility semiconducting polymer poly(N,N-bis-2-octyldodecylnaphthalene-1,4,5,8-bis-dicarboximide-2,6-diyl-alt-5,5-2,2-bithiophene) (P(NDI2OD-T2)) are probed using a combination of grazing-incidence wide-angle X-ray scattering (GIWAXS) and near-edge X-ray absorption fine-structure (NEXAFS) spectroscopy. In particular a novel approach is used whereby the bulk molecular orientation and surface molecular orientation are simultaneously measured on the same sample using NEXAFS spectroscopy in an angle-resolved transmission experiment. Furthermore, the acquisition of bulk-sensitive NEXAFS data enables a direct comparison of the information provided by GIWAXS and NEXAFS. By comparison of the bulk-sensitive and surface-sensitive NEXAFS data, a distinctly different molecular orientation is observed at the surface of the film compared to the bulk. While a more "face-on" orientation of the conjugated backbone is observed in the bulk of the film, consistent with the lamella orientation observed by GIWAXS, a more "edge-on" orientation is observed at the surface of the film with surface-sensitive NEXAFS spectroscopy. This distinct edge-on surface orientation explains the high in-plane mobility that is achieved in top-gate P(NDI2OD-T2) field-effect transistors (FETs), while the bulk face-on texture explains the high out-of-plane mobilities that are observed in time-of-flight and diode measurements. These results also stress that GIWAXS lacks the surface sensitivity required to probe the microstructure of the accumulation layer that supports charge transport in organic FETs and hence may not necessarily be appropriate for correlating film microstructure and FET charge transport.

  19. Conjugates of methylated cyclodextrin derivatives and hydroxyethyl starch (HES: Synthesis, cytotoxicity and inclusion of anaesthetic actives

    Directory of Open Access Journals (Sweden)

    Lisa Markenstein

    2014-12-01

    Full Text Available The mono-6-deoxy-6-azides of 2,6-di-O-methyl-β-cyclodextrin (DIMEB and randomly methylated-β-cyclodextrin (RAMEB were conjugated to propargylated hydroxyethyl starch (HES by Cu+-catalysed [2 + 3] cycloaddition. The resulting water soluble polymers showed lower critical solution temperatures (LCST at 52.5 °C (DIMEB-HES and 84.5 °C (RAMEB-HES, respectively. LCST phase separations could be completely avoided by the introduction of a small amount of carboxylate groups at the HES backbone. The methylated CDs conjugated to the HES backbone exhibited significantly lower cytotoxicities than the corresponding monomeric CD derivatives. Since the binding potentials of these CD conjugates were very high, they are promising candidates for new oral dosage forms of anaesthetic actives.

  20. Strong Composition Effects in All-Polymer Phototransistors with Bulk Heterojunction Layers of p-type and n-type Conjugated Polymers.

    Science.gov (United States)

    Han, Hyemi; Lee, Chulyeon; Kim, Hwajeong; Seo, Jooyeok; Song, Myeonghun; Nam, Sungho; Kim, Youngkyoo

    2017-01-11

    We report the composition effect of polymeric sensing channel layers on the performance of all-polymer phototransistors featuring bulk heterojunction (BHJ) structure of electron-donating (p-type) and electron-accepting (n-type) polymers. As an n-type component, poly(3-hexylthiopehe-co-benzothiadiazole) end-capped with 4-hexylthiophene (THBT-4ht) was synthesized via two-step reactions. A well-studied conjugated polymer, poly(3-hexylthiophene) (P3HT), was employed as a p-type polymer. The composition of BHJ (P3HT:THBT-4ht) films was studied in detail by varying the THBT-4ht contents (0, 1, 3, 5, 10, 20, 30, 40, and 100 wt %). The best charge separation in the P3HT:THBT-4ht films was measured at 30 wt % by the photoluminescence (PL) study, while the charge transport characteristics of devices were improved at the low THBT-4ht contents (polymer phototransistors was higher than that of the phototransistors with the pristine P3HT layers and strongly dependent on the BHJ composition. The highest (corrected) responsivity (RC) was achieved at 20 wt %, which can be attributable to the balance between the best charge separation and transport states, as investigated for crystal nanostructures and surface morphology by employing synchrotron-radiation grazing-incidence wide-angle X-ray scattering, high-resolution/scanning transmission electron microscopy, and atomic force microscopy.

  1. Photoresist-Free Patterning by Mechanical Abrasion of Water-Soluble Lift-Off Resists and Bare Substrates: Toward Green Fabrication of Transparent Electrodes

    OpenAIRE

    Adam D Printz; Esther Chan; Celine Liong; René S Martinez; Lipomi, Darren J.

    2013-01-01

    This paper describes the fabrication of transparent electrodes based on grids of copper microwires using a non-photolithographic process. The process--"abrasion lithography"--takes two forms. In the first implementation (Method I), a water-soluble commodity polymer film is abraded with a sharp tool, coated with a conductive film, and developed by immersion in water. Water dissolves the polymer film and lifts off the conductive film in the unabraded areas. In the second implementation (Method ...

  2. Synthesis and studies of water-soluble Prussian Blue-type nanoparticles into chitosan beads.

    Science.gov (United States)

    Folch, Benjamin; Larionova, Joulia; Guari, Yannick; Molvinger, Karine; Luna, Carlos; Sangregorio, Claudio; Innocenti, Claudia; Caneschi, Andrea; Guérin, Christian

    2010-10-21

    A new approach to the synthesis of highly stable aqueous colloids of coordination polymer nanoparticles was developed by using water-soluble chitosan beads as template and as stabilizing agent. The method consists in the synthesis of nanocomposite beads containing cyano-bridged coordination polymer nanoparticles via step-by-step coordination of the metal ions and the hexacyanometallate precursors into the chitosan pores and then water solubilization of these as-obtained nanocomposite beads. We obtain a large range of M(2+)/[M'(CN)(6)](3-)/chitosan (where M(2+) = Ni(2+), Cu(2+), Fe(2+), Co(2+), Mn(2+) and M' = Fe(3+) and Cr(3+)) nanocomposite beads and their respective aqueous colloids containing coordination polymer core/chitosan shell nanoparticles. The nanocomposite beads and the corresponding aqueous colloids were studied by Infrared (IR) and UV-Vis spectroscopy, nitrogen sorption (BET), Transmission Electron Microscopy (TEM), High Resolution Transmission Electron Microscopy (HRTEM) and magnetic analyses, which reveal the presence of homogeneously dispersed uniformly-sized cyano-bridged coordination polymer nanoparticles. The detailed studies of the static and dynamic magnetic properties of these nanoparticles show the occurrence of a spin-glass like behavior presumably produced by intra-particle spin disorder due to the low spin exchange energy characterizing these materials.

  3. Processing Cyclic Peptide-polymer Conjugates in Block Copolymer Thin Films for Sub-nm Porous Membranes

    Science.gov (United States)

    Zhang, Chen; Xu, Ting

    2014-03-01

    Porous thin films containing subnanometer channels oriented normal to the surface exhibit unique transport and separation properties and can serve as selective membranes for separation. Inspired by natural protein channels, we have developed an approach using cyclic peptide nanotubes (CPNs) embedded in polymeric matrix to mimic the transport of natural channels. The co-assembly of polymer-covered CPNs in a block copolymer (BCP) thin film requires the synchronization of two self-assembly processes, namely the microphase separation of BCP and the nanotube growth of CP-polymer conjugates. We systematically investigated the co-assembly of isolated CP-poly(ethylene glycol) (CP-PEG) conjugates and polystyrene-b-poly (methyl methacrylate) (PS-b-PMMA) in thin films as a function of CP-PEG loading (fCP-PEG) and solvent-polymer interactions. We find that there is a strong dependence of the co-assembly process on fCP-PEG due to thermodynamic limit of incorporating one CPN in one PMMA microdomain, as well as the kinetic pathway in which favorable PEG-solvent interaction helps to disperse CPNs and thus lowers the activation energy barrier of the system. This study presents critical insights in guided assemblies of functional building blocks within nanoscopic frameworks. DOE-EFRC-Gas Separation, Army Research Office.

  4. Do the Defects Make It Work? Defect Engineering in Pi-Conjugated Polymers and Their Solar Cells: Preprint

    Energy Technology Data Exchange (ETDEWEB)

    Wang, D.; Reese, M.; Kopidakis N.; Gregg, B. A.

    2008-05-01

    The charged defect density in common pi-conjugated polymers such as poly(3-hexylthiophene), P3HT, is around 1018 cm-3. Despite, or perhaps because of, this huge defect density, bulk heterojunction solar cells made from these polymers and a C60 derivative such as PCBM exhibit some of the highest efficiencies (~5%) yet obtained in solid state organic photovoltaic cells. We discuss defects in molecular organic semiconductors and in pi-conjugated polymers. These defects can be grouped in two categories, covalent and noncovalent. Somewhat analogous to treating amorphous silicon with hydrogen, we introduce chemical methods to modify the density and charge of the covalent defects in P3HT by treating it with electrophiles such as dimethyl sulfate and nucleophiles such as sodium methoxide. The effects of these treatments on the electrical and photovoltaic properties and stability of organic PV cells is discussed in terms of the change in the number and chemical properties of the defects. Finally, we address the question of whether the efficiency of OPV cells requires the presence of these defects which function as adventitious p-type dopants. Their presence relieves the resistance limitations usually encountered in cleaner organic semiconductors and can create built-in electric fields at junctions.

  5. Buta-1,3-diyne-Based π-Conjugated Polymers for Organic Transistors and Solar Cells

    Energy Technology Data Exchange (ETDEWEB)

    Eckstein, Brian J.; Melkonyan, Ferdinand S.; Zhou, Nanjia; Manley, Eric F.; Smith, Jeremy; Timalsina, Amod; Chang, Robert P. H.; Chen, Lin X.; Facchetti, Antonio; Marks, Tobin J.

    2017-02-09

    We report the synthesis and characterization of new alkyl-substituted 1,4-di(thiophen-2-yl)buta-1,3-diyne (R-DTB) donor building blocks, based on the -C≡C-C≡C- conjugative pathway, and their incorporation with thienyl-diketopyrrolopyrrole (R'-TDPP) acceptor units into π-conjugated PTDPP-DTB polymers (P1-P4). The solubility of the new polymers strongly depends on the DTB and DPP solubilizing (R and R', respectively) substituents. Thus, solution processable and high molecular weight PDPP-DTB polymers are achieved for P3 (R = n-C12H25, R' = 2- butyloctyl) and P4 (R = 2-ethylhexyl, R' = 2-butyloctyl). Systematic studies of P3 and P4 physicochemical properties are carried using optical spectroscopy, cyclic voltammetry, and thermal analysis, revealing characteristic features of the dialkynyl motif. For the first time, optoelectronic devices (OFETs, OPVs) are fabricated with 1,3-butadiyne containing organic semiconductors. OFET hole mobilities and record OPV power conversion efficiencies for acetylenic organic materials approach 0.1 cm2/(V s) and 4%, respectively, which can be understood from detailed thin-film morphology and microstructural characterization using AFM, TEM, XRD, and GIWAXS methodologies. Importantly, DTB-based polymers (P3 and P4) exhibit, in addition to stabilization of frontier molecular orbitals and to -C≡C-C≡C- relief of steric torsions, discrete morphological pliability through thermal annealing and processing additives. The advantageous materials properties and preliminary device performance reported here demonstrate the promise of 1,3-butadiyne-based semiconducting polymers.

  6. 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

  7. 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.

  8. Preliminary evaluation of a water soluble chlorin photosensitizer

    Science.gov (United States)

    Zou, Jian; Huang, Qiuyan; Li, Weijun; Zou, Shulin; Han, Zhen; Huang, Zheng

    2017-07-01

    Some of the key optical properties of a new water soluble chlorine (YLG-1) were evaluated. The sensitizer has a strong absorption at 398 nm and 655 nm in DMSO. A strong red fluorescence is detected under the excitation of 398 nm. The fluorescence life time is approximately 5 ns and fluorescence quantum yield 20%. The sensitizer does not accumulate in normal skin after topical use or IV injection. Preliminary in vivo results suggest that this novel chlorine causes little cutaneous phototoxicity. Its potentials in photodynamic therapy (PDT) deserve further study.

  9. Determination of Carboxylic Acids and Water-soluble Inorganic Ions ...

    African Journals Online (AJOL)

    The results showed that mean mass concentration of PM2.5 and PM10 were 13 ± 3.5 μg m–3 and 16 ± 2.3 μg m–3, respectively. Mean concentrations of the total carboxylates were 23.7±6.5 ngm–3 in PM2.5 and 36.4 ± 12 ngm–3 in PM10 whereas total water-soluble inorganic ions were 448±88 ngm–3 and 646± 214 ...

  10. Water-soluble magnetic nanoparticles with biologically active stabilizers

    Science.gov (United States)

    Zablotskaya, Alla; Segal, Izolda; Lukevics, Edmunds; Maiorov, Mikhail; Zablotsky, Dmitry; Blums, Elmars; Shestakova, Irina; Domracheva, Ilona

    2009-05-01

    We present the results of the interaction of iron oxide nanoparticles with some biologically active surfactants, namely, oleic acid and cytotoxic alkanolamine derivatives. Physico-chemical properties, as magnetization, magnetite concentration and particle diameter, of the prepared magnetic samples were studied. The nanoparticle size of 11 nm for toluene magnetic fluid determined by TEM is in good agreement with the data obtained by the method of magnetogranulometry. In vitro cytotoxic effect of water-soluble nanoparticles with different iron oxide:oleic acid molar ratio were revealed against human fibrosarcoma and mouse hepatoma cells. In vivo results using a sarcoma mouse model showed observable antitumor action.

  11. Water-soluble magnetic nanoparticles with biologically active stabilizers

    Energy Technology Data Exchange (ETDEWEB)

    Zablotskaya, Alla [Latvian Institute of Organic Synthesis, 21 Aizkraukles Street, Riga LV-1006 (Latvia)], E-mail: aez@osi.lv; Segal, Izolda; Lukevics, Edmunds [Latvian Institute of Organic Synthesis, 21 Aizkraukles Street, Riga LV-1006 (Latvia); Maiorov, Mikhail; Zablotsky, Dmitry; Blums, Elmars [Institute of Physics, University of Latvia, 32 Miera, Salaspils LV-2169 (Latvia); Shestakova, Irina; Domracheva, Ilona [Latvian Institute of Organic Synthesis, 21 Aizkraukles Street, Riga LV-1006 (Latvia)

    2009-05-15

    We present the results of the interaction of iron oxide nanoparticles with some biologically active surfactants, namely, oleic acid and cytotoxic alkanolamine derivatives. Physico-chemical properties, as magnetization, magnetite concentration and particle diameter, of the prepared magnetic samples were studied. The nanoparticle size of 11 nm for toluene magnetic fluid determined by TEM is in good agreement with the data obtained by the method of magnetogranulometry. In vitro cytotoxic effect of water-soluble nanoparticles with different iron oxide:oleic acid molar ratio were revealed against human fibrosarcoma and mouse hepatoma cells. In vivo results using a sarcoma mouse model showed observable antitumor action.

  12. [Antibacterial activity of water soluble fraction from Scolopendra subspinipes mutilans].

    Science.gov (United States)

    Ren, Wen-hua; Zhang, Shuang-quan; Song, Da-xiang; Zhou, Kai-ya

    2007-01-01

    The water soluble fraction (SWSF) of centipede Scolopendra subspinipes mautilans, injected with Escherichia coli K12 D31 for 3-4 days showed broad-spectrum antimicrobial activity against Gram-positive, Gram-negative bacteria and fungi. It showed strong antibacterial activity against E. coli K12D31 at different temperatures, pH and ionic strengths. It did not show any hemolytic and agglutination activities at the concentration below 600 microg/ml. After E. coli K12 D31 treated with SWSF, the ultrastructure showed that its outer cell wall was broken, surface collapsed and intracellular substances leaked out.

  13. 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...... on the benzene ring where power conversion efficiencies of up to 3.6% were achieved. All studied materials were prepared with an objective of low-cost starting materials, simple synthesis, and simple processing conditions which was most successful for the polymer P5. The polymer P7 containing fluorine atoms...... results were corroborated with full optical and morphological characterization of the conjugated polymers. We conclude that the determination of the best anchoring position for the side chains is the most rational starting point for the optimization of a polymer with a potential for large...

  14. Synthesis of poly(ethylene glycol)-polydiacetylene conjugates and their micellar and chromic characteristics.

    Science.gov (United States)

    Choi, Hye; Bae, Yun Mi; Yu, Gwang Sig; Huh, Kang Moo; Choi, Joon Sig

    2008-10-01

    In this report, novel polymer-lipid conjugates were synthesized and their unique micellar and chromic properties were studied. The conjugates were synthesized by the liquid-phase peptide synthesis method using methoxy(polyethylene glycol)-amine (mPEG-NH2, MW2000) as a supporting material. One and two 10,12-pentacosadiynoic acid (PCDA) groups were conjugated to mPEG-NH2 to prepare mPEG-PCDA and mPEG-PCDA2, respectively. The polymer conjugates could form nanometer-sized micelles in aqueous media and be further polymerized under the exposure of UV 254 nm due to the UV sensitive nature of PCDA. It was observed that mPEG-PCDA2 micelle showed very distinctive photochromism and thermochromism in response to UV or heat, whereas mPEG-PCDA did not display any chromic properties. Moreover, a distinctive chromic property change was observed by adding alpha-cyclodextrin as a model biological molecule to the micelle solution. Due to their unique properties such as high water-solubility, cross-linkable micelle formation with a nano-scaled size, and stimuli-responsive chromic nature, the polymer-lipid conjugates would be useful for various biomedical applications, in particular as a nano-carrier for drug delivery and biosensor.

  15. 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.

  16. A Conjugated Microporous Polymer for Palladium-Free, Visible Light-Promoted Photocatalytic Stille-Type Coupling Reactions.

    Science.gov (United States)

    Ghasimi, Saman; Bretschneider, Simon A; Huang, Wei; Landfester, Katharina; Zhang, Kai A I

    2017-08-01

    The Stille coupling reaction is a versatile method to mainly form aromatic C-C bonds. However, up to now, the use of palladium catalysts is necessary. Here, a palladium-free and photocatalytic Stille-type coupling reaction of aryl iodides and aryl stannanes catalyzing a conjugated microporous polymer-based phototcatalyst under visible light irradiation at room temperature is reported. The novel coupling reaction mechanism occurs between the photogenerated aryl radical under oxidative destannylation of the aryl stannane, and the electron-activated aryl iodide, resulting into the aromatic C-C bond formation reaction. The visible light-promoted Stille-type coupling reaction using the polymer-based pure organic photocatalyst offers a simple, sustainable, and more economic synthetic pathway toward palladium-free aromatic C-C bond formation.

  17. Therapeutic Effects of Water Soluble Danshen Extracts on Atherosclerosis

    Directory of Open Access Journals (Sweden)

    Yoon Hee Cho

    2013-01-01

    Full Text Available Danshen is a traditional Chinese medicine with many beneficial effects on cardiovascular diseases. The aim of this study was to evaluate the mechanisms responsible for the antiatherogenic effect of water soluble Danshen extracts (DEs. Rat vascular smooth muscle cells (VSMCs and human umbilical vein endothelial cells (HUVECs were treated with DE. To evaluate the effects of DE in vivo, carotid balloon injury and tail vein thrombosis were induced in Sprague-Dawley (SD rats and iliac artery stent was induced in New Zealand white rabbits. The inhibitory action of DE on platelet aggregation was confirmed with an impedance aggregometer. DE inhibited the production of reactive oxygen species, and the migration and proliferation of platelet-derived growth factor-BB stimulated VSMCs. Furthermore, DE prevented inflammation and apoptosis in HUVECs. Both effects of DE were reconfirmed in both rat models. DE treatment attenuated platelet aggregation in both in vivo and ex vivo conditions. Pretreatment with DE prevented tail vein thrombosis, which is normally induced by κ-carrageenan injection. Lastly, DE-treated rabbits showed decreased in-stent restenosis of stented iliac arteries. These results suggest that water soluble DE modulates key atherogenic events in VSMCs, endothelial cells, and platelets in both in vitro and in vivo conditions.

  18. Synthesis and anticancer properties of water-soluble zinc ionophores.

    Science.gov (United States)

    Magda, Darren; Lecane, Philip; Wang, Zhong; Hu, Weilin; Thiemann, Patricia; Ma, Xuan; Dranchak, Patricia K; Wang, Xiaoming; Lynch, Vincent; Wei, Wenhao; Csokai, Viktor; Hacia, Joseph G; Sessler, Jonathan L

    2008-07-01

    Several water-solubilized versions of the zinc ionophore 1-hydroxypyridine-2-thione (ZnHPT), synthesized as part of the present study, have been found both to increase the intracellular concentrations of free zinc and to produce an antiproliferative activity in exponential phase A549 human lung cancer cultures. Gene expression profiles of A549 cultures treated with one of these water-soluble zinc ionophores, PCI-5002, reveal the activation of stress response pathways under the control of metal-responsive transcription factor 1 (MTF-1), hypoxia-inducible transcription factor 1 (HIF-1), and heat shock transcription factors. Additional oxidative stress response and apoptotic pathways were activated in cultures grown in zinc-supplemented media. We also show that these water-soluble zinc ionophores can be given to mice at 100 micromol/kg (300 micromol/m(2)) with no observable toxicity and inhibit the growth of A549 lung and PC3 prostate cancer cells grown in xenograft models. Gene expression profiles of tumor specimens harvested from mice 4 h after treatment confirmed the in vivo activation of MTF-1-responsive genes. Overall, we propose that water-solubilized zinc ionophores represent a potential new class of anticancer agents.

  19. Preparation and Characterization of Water-Soluble Xylan Ethers

    Directory of Open Access Journals (Sweden)

    Kay Hettrich

    2017-03-01

    Full Text Available Xylan is a predominant hemicellulose component that is found in plants and in some algae. This polysaccharide is made from units of xylose (a pentose sugar. One promising source of xylan is oat spelt. This feedstock was used for the synthesis of two xylan ethers. To achieve water soluble products, we prepared dihydroxypropyl xylan as a non-ionic ether on the one hand, and carboxymethyl xylan as an ionic derivative on the other hand. Different preparation methods like heterogeneous, pseudo-homogeneous, and homogeneous syntheses were compared. In the case of dihydroxypropyl xylan, the synthesis method did not significantly affect the degree of substitution (DS. In contrast, in the case of carboxymethyl xylan, clear differences of the DS values were found in dependence on the synthesis method. Xylan ethers with DS values of >1 could be obtained, which mostly show good water solubility. The synthesized ionic, as well as non-ionic, xylan ethers were soluble in water, even though the aqueous solutions showed slight turbidity. Nevertheless, stable, transparent, and stainable films could be prepared from aqueous solutions from carboxymethyl xylans.

  20. 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.