Science.gov

Sample records for conjugated polymer films

  1. Semiconductor-nanocrystal/conjugated polymer thin films

    DOEpatents

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

    2014-06-17

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

  2. Semiconductor-nanocrystal/conjugated polymer thin films

    DOEpatents

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

    2010-08-17

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

  3. Microwave absorption of free carriers in doped conjugated polymer films

    NASA Astrophysics Data System (ADS)

    Rumbles, Garry

    Flash photolysis time-resolved microwave conductivity (fp-TRMC) is a powerful spectroscopic tool for the detection of mobile charges in organic systems, such as conjugated polymers. We will report on a study of charge carrier generation in a number of polymer systems where the solid-state microstructure (SSM) of the thin films can be controlled using both molecular structure and processing conditions. By incorporating a low concentration of molecular acceptors, such as metallo-phthalocyanines, as well as substituted fullerenes and perylenes, the driving force for photoinduced electron transfer can be controlled through the excited state energy and the reduction potential. Our results indicate the importance of the crystalline phase of the polymer to stabilise and reduce the rate of recombination of the holes with the electrons that remain trapped on the acceptor. In addition, the role that the SSM plays on the stabilization of bound electron-hole pairs, or charge-transfer (CT) states will be examined.

  4. Electrochemically polymerized conjugated polymer films: Stability improvement and surface functionalization

    NASA Astrophysics Data System (ADS)

    Wei, Bin

    Conjugated polymers have been widely used in various applications including organic solar cells, electrochromic devices, chemical sensors, and biomedical devices. Poly(3,4-ethylenedioxythiophene) (PEDOT) and its derivatives have received considerable interest because of their low oxidation potential, relatively high chemical stability, and high conductivity. Electrochemical deposition is a convenient method for precisely fabricating conjugated polymer thin films. Here, we report the stability improvement and surface functionalization of electrochemically polymerized PEDOT films. The long-term performance of PEDOT coatings is limited by their relatively poor stability on various inorganic substrates. Two different methods were used to improve the stability of PEDOT coatings, one involved using carboxylic acid functionalized EDOT (EDOT-acid) as adhesion promoter. EDOT-acid molecules were chemically bonded onto activated metal oxide substrates via chemisorption. PEDOT was then polymerized onto the EDOT-acid modified substrates, forming covalently bonded coatings. An aggressive ultrasonication test confirmed the significantly improved adhesion of the PEDOT films on electrodes with EDOT-acid treatment over those without treatment. The other method was to use an octa-ProDOT-functionalized POSS derivative (POSSProDOT) as cross-linker. PEDOT copolymer films were electrochemically deposited with various concentrations of POSS-ProDOT. The optical, morphological and electrochemical properties of the copolymer films could be systematically tuned with the incorporation of POSS-ProDOT. Significantly enhanced electrochemical and mechanical stability of the copolymers were observed at intermediate levels of POSS-ProDOT content (3.1 wt%) via chronic stimulation tests. Surface functionalization of conducting polymer films provides a potential means for systematically tailoring their chemical and physical properties. We have synthesized, polymerized and characterized a dialkene

  5. Nanoparticles of conjugated polymers prepared from phase-separated films of phospholipids and polymers for biomedical applications.

    PubMed

    Yoon, Jungju; Kwag, Jungheon; Shin, Tae Joo; Park, Joonhyuck; Lee, Yong Man; Lee, Yebin; Park, Jonghyup; Heo, Jung; Joo, Chulmin; Park, Tae Jung; Yoo, Pil J; Kim, Sungjee; Park, Juhyun

    2014-07-09

    Phase separation in films of phospholipids and conjugated polymers results in nanoassemblies because of a difference in the physicochemical properties between the hydrophobic polymers and the polar lipid heads, together with the comparable polymer side-chain lengths to lipid tail lengths, thus producing nanoparticles of conjugated polymers upon disassembly in aqueous media by the penetration of water into polar regions of the lipid heads.

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

    PubMed

    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.

  7. Cellulose nanofibril based graft conjugated polymer films act as a chemosensor for nitroaromatic.

    PubMed

    Niu, Qingyuan; Gao, Kezheng; Wu, Wenhui

    2014-09-22

    A cellulose nanofibril film is modified by chemical assembly of boronate-terminated conjugated polymer chains at its specific sites, C-6 carboxyl groups. The modified cellulose nanofibril film is used as a fluorescent sensor for nitroaromatic vapor. Thanks to the specific reactive sites, numerous loose cavities or pathways located in the film sensor's out-layer have been formed, and the fraction of easily accessible cavities of the novel fluorescent film sensor is up to 0.97, which could benefit the penetration and diffusion of analyte vapor. Therefore, the novel fluorescent film sensor exhibits high sensitivity toward nitroaromatic vapor with a fast response. The fluorescence quenching efficiency of the chemical-assembly film sensor is about 3 times larger than that of the spin-cast film sensor using the same conjugated polymer for 600 s exposure to DNT vapor. In addition, the novel fluorescent film sensor shows good reversibility.

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

    NASA Astrophysics Data System (ADS)

    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

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

    NASA Astrophysics Data System (ADS)

    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.

  10. Deviations of the glass transition temperature in amorphous conjugated polymer thin films

    NASA Astrophysics Data System (ADS)

    Liu, Dan; Osuna Orozco, Rodrigo; Wang, Tao

    2013-08-01

    The deviations of the glass transition temperature (Tg) in thin films of an amorphous conjugated polymer poly(9,9-dioctylfluorene-co-N-(4-butylphenyl)diphenylamine) (TFB) are reported. Monotonic and nonmonotonic Tg deviations are observed in TFB thin films supported on Si-SiOx and poly(3,4-ethylenedioxythiophene) poly(styrenesulfonate) (PEDOT:PSS), respectively. A three-layer model is developed to fit both monotonic and nonmonotonic Tg deviations in these films. A 5-nm PEDOT:PSS capping layer was not found to be effective to remove the free-surface effect in Si-SiOx supported TFB films.

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

    NASA Astrophysics Data System (ADS)

    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.

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

    PubMed Central

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

    2015-01-01

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

  13. Mimicking Conjugated Polymer Thin Film Photophysics with a Well-Defined Triblock Copolymer in Solution

    SciTech Connect

    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.

  14. Mimicking conjugated polymer thin-film photophysics with a well-defined triblock copolymer in solution.

    PubMed

    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.

  15. Electrochemical spectroscopy of conjugated polymers

    NASA Astrophysics Data System (ADS)

    Hwang, Jungseek

    Conjugated polymers become conductors when they are doped (oxidized or reduced). The initial work was done on conducting polymers by three Nobel laureates (A. J. Heeger, H. Shirakawa, and A. G. MacDiarmid) in 1977. They discovered an increase by nearly 10 orders of magnitude in the electrical conductivity of polyacetylene when it was doped with iodine or other acceptors. Conjugated polymers have been studied intensively since that time because of their high conductivity, reversible doping and low-dimensional geometry. Doping causes electronic structure changes which have numerous potential applications. We have studied three thiophene derivative polymers: poly (3,4-ethylenedioxy-thiophene) (PEDOT), poly (3,4-propylenedioxythiophene) (PProDOT), and poly (3,4-dimethylpropylenedioxythiophene) (PProDOTMe2). Two types of samples were used for this study. The first was a thin polymer film on an indium tin oxide (ITO) coated glass slide. The polymer film was deposited on a metallic ITO surface by an electrochemical method. We measured reflectance and transmittance of the sample. The data were analyzed by modeling all layers of this multi-layer thin film structure, using the Drude-Lorentz model for each layer. We calculated the optical constants from the modeling results and obtained information on the electronic structure of the neutral and doped polymers. Conjugated polymers can be reversibly doped in an electrochemical cell. The doping causes optical absorption bands to move from one optical frequency to another frequency. To study this behavior, we prepared another type of sample. First, a thin polymer film was deposited on a gold-coated Mylar film by the same electrochemical method. Then, we built electrochromic cells with an infrared transparent window, using the polymer films on the gold/Mylar strips as electrodes. We connected the cell to an electrical supply. As we change the cell voltage (potential difference between the two electrodes), we can change the doping

  16. Aqueous dispersion of conjugated polymers by colloidal clays and their film photoluminescence.

    PubMed

    Lan, Yi-Fen; Lee, Rong-Ho; Lin, Jiang-Jen

    2010-02-11

    The plate-shaped clays enabled us to disperse water-insoluble conjugated polymers (CPs) into a colloidal form and an aqueous process for making CP films. Simple pulverization of poly[2-methoxy-5-(2'-ethylhexyloxy)-1,4-phenylenevinylene] (MEH-PPV) with silicate clays rendered the powder mixture an unusual dispersing behavior in water. The most effective clay was selected from screening several natural and synthetic clays including synthetic fluorinated mica (Mica), sodium montmorillonite (MMT), synthetic smectite (SWN), and cationic layered double hydroxide (LDH). A high aspect ratio and intensive charge density (2.1 e nm(-1)) of Mica were highly effective for promoting the CP dispersion. The enhancement for dispersing MEH-PPV is rated in the following trend: Mica > MMT > SWN > LDH. The result is rationalized by the influences of their geometric shape and ionic charge of clay on MEH-PPV in water. Two other representative CPs, sulfonated polyaniline (SPA) and triphenyl phosphine oxide cored polyaniline (TPOPA), were used to generalize the CP/clay colloidal behavior. All of the three CPs as in an aqueous form can be coated into hybrid films. Under an ultraviolet lamp, these films showed color emissions, orange for MEH-PPV/Mica, olive for SPA/Mica, and green for TPOPA/Mica, which are consistent with the photoluminescence measurements.

  17. Controlled synthesis of conjugated microporous polymer films: versatile platforms for highly sensitive and label-free chemo- and biosensing.

    PubMed

    Gu, Cheng; Huang, Ning; Gao, Jia; Xu, Fei; Xu, Yanhong; Jiang, Donglin

    2014-05-05

    Conjugated microporous polymers (CMPs), in which rigid building blocks form robust networks, are usually synthesized as insoluble and unprocessable powders. We developed a methodology using electropolymerization for the synthesis of thin CMP films. The thickness of these films is synthetically controllable, ranging from nanometers to micrometers, and they are obtained on substrates or as freestanding films. The CMP films combine a number of striking physical properties, including high porosity, extended π conjugation, facilitated exciton delocalization, and high-rate electron transfer. We explored the CMP films as versatile platforms for highly sensitive and label-free chemo- and biosensing of electron-rich and electron-poor arenes, metal ions, dopamine, and hypochloroic acid, featuring rapid response, excellent selectivity, and robust reusability.

  18. Polymer films

    DOEpatents

    Granick, Steve; Sukhishvili, Svetlana A.

    2004-05-25

    A film contains a first polymer having a plurality of hydrogen bond donating moieties, and a second polymer having a plurality of hydrogen bond accepting moieties. The second polymer is hydrogen bonded to the first polymer.

  19. Polymer films

    DOEpatents

    Granick, Steve; Sukhishvili, Svetlana A.

    2008-12-30

    A film contains a first polymer having a plurality of hydrogen bond donating moieties, and a second polymer having a plurality of hydrogen bond accepting moieties. The second polymer is hydrogen bonded to the first polymer.

  20. Fluorescence enhancement of the conjugated polymer films based on well-ordered Au nanoparticle arrays

    NASA Astrophysics Data System (ADS)

    Zhong, Benbin; Zu, Xihong; Yi, Guobin; Huang, Hailiang; Zhang, Minghai; Luo, Hongsheng

    2016-09-01

    In this paper, well-ordered Au nanoparticle arrays on silicon substrates were employed as efficient metal-enhanced fluorescence (MEF) substrates for investigating the fluorescence properties of the conjugated polymer poly(3-hexylthiophene) (P3HT). The ordered Au nanoparticle arrays were fabricated by block copolymer self-assembly technology, and the particle sizes were controlled by adjusting the molar ratios of HAuCl4 precursor to vinyl pyridine units. The approach is economical and suitable to fabricate large-area MEF substrates. The results about fluorescence properties of P3HT showed that the fluorescence intensities of the P3HT films were improved on ordered Au nanoparticle arrays compared to those on bare silicon substrate and were significantly enhanced with the Au nanoparticle sizes increasing. The mechanism is based on localized surface plasmon resonances, coupling and propagating surface plasmons, and the emission enhancement mainly resulted from the increase of the excitation rate. This work provides a new way to prepare efficient MEF substrates for high-performance fluorescence-based devices.

  1. Covalent polymer-drug conjugates.

    PubMed

    Elvira, Carlos; Gallardo, Alberto; Roman, Julio San; Cifuentes, Alejandro

    2005-01-31

    In this work, polymer-drugs conjugates used as drug delivery systems (DDS) are revised attending to their chemical conjugation. Namely, the classification of this type of DDS is based on the conjugation sites of the reactive groups (i.e., via end groups or pendant polymer groups). Advantages and limitations of these types of DDS are discussed through representative examples of polymer-drugs and polymer-proteins conjugates recently developed.

  2. Processing Cyclic Peptide-polymer Conjugates in Block Copolymer Thin Films for Sub-nm Porous Membranes

    NASA Astrophysics Data System (ADS)

    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.

  3. Synthesis of cyanopyridine based conjugated polymer

    PubMed Central

    Hemavathi, B.; Ahipa, T.N.; Pillai, Saju; Pai, Ranjith Krishna

    2016-01-01

    This data file contains the detailed synthetic procedure for the synthesis of two new cyanopyridine based conjugated polymer P1 and P2 along with the synthesis of its monomers. The synthesised polymers can be used for electroluminescence and photovoltaic (PV) application. The physical data of the polymers are provided in this data file along with the morphological data of the polymer thin films. The data provided here are in association with the research article entitled ‘Cyanopyridine based conjugated polymer-synthesis and characterisation’ (Hemavathi et al., 2015) [3]. PMID:27158642

  4. Influence of Morphological Disorder on In- and Out-of-Plane Charge Transport in Conjugated Polymer Films

    NASA Astrophysics Data System (ADS)

    Dong, Ban; Li, Anton; Green, Peter

    We report the unequal impacts of morphological disorder on in- and out-of-plane charge transport in thin films of poly(3-hexylthiophene) (P3HT) fabricated by both conventional spin-casting and the novel technique Matrix-Assisted Pulsed Laser Evaporation (MAPLE). MAPLE produces films with inhomogeneous globular subfeatures with dimensions on the order of 100 nm. Optical absorbance spectroscopy corroborates that MAPLE-deposited films are more energetically disordered, but possesses average conjugation lengths comparable to spin-cast P3HT. Both in- and out-of-plane carrier transport measurements of MAPLE-deposited films show characteristics that reflect a higher degree of energetic disorder and broadened density of states. Whereas in-plane carrier mobilities of MAPLE-deposited thin-film transistors are comparable to spin-cast analogues (8.3 x 10-3 cm2V-1s-1 versus 5.5 x 10-3 cm2V-1s-1) , the out-of-plane mobilities of MAPLE-deposited samples are nearly an order of magnitude lower (4.1 x 10-4 cm2V-1s-1 versus 2.7 x 10-3 cm2V-1s-1) . The unusual ensemble of properties and behaviors arising from the unique morphologies produced by MAPLE provide important perspectives on the extent to which disorder impacts different mechanisms of charge transport in conjugated polymers.

  5. Molecular organization in MAPLE-deposited conjugated polymer thin films and the implications for carrier transport characteristics

    SciTech Connect

    Dong, Ban Xuan; Li, Anton; Strzalka, Joseph; Stein, Gila E.; Green, Peter F.

    2016-09-18

    The morphological structure of poly(3-hexylthiophene) (P3HT) thin films deposited by both Matrix Assisted Pulsed Laser Evaporation (MAPLE) and solution spin-casting methods are investigated. We found that the MAPLE samples possessed a higher degree of disorder, with random orientations of polymer crystallites along the side-chain stacking, π-π stacking, and conjugated backbone directions. Furthermore, the average molecular orientations and relative degrees of crystallinity of MAPLE-deposited polymer films are insensitive to the chemistries of the substrates onto which they were deposited; this is in stark contrast to the films prepared by the conventional spin-casting technique. In spite of the seemingly unfavorable molecular orientations and the highly disordered morphologies, the in-plane charge carrier transport characteristics of the MAPLE samples are comparable to those of spin-cast samples, exhibiting similar transport activation energies (56 meV versus 54 meV) to those reported in the literature for high mobility polymers.

  6. Molecular organization in MAPLE-deposited conjugated polymer thin films and the implications for carrier transport characteristics

    DOE PAGES

    Dong, Ban Xuan; Li, Anton; Strzalka, Joseph; ...

    2016-09-18

    The morphological structure of poly(3-hexylthiophene) (P3HT) thin films deposited by both Matrix Assisted Pulsed Laser Evaporation (MAPLE) and solution spin-casting methods are investigated. We found that the MAPLE samples possessed a higher degree of disorder, with random orientations of polymer crystallites along the side-chain stacking, π-π stacking, and conjugated backbone directions. Furthermore, the average molecular orientations and relative degrees of crystallinity of MAPLE-deposited polymer films are insensitive to the chemistries of the substrates onto which they were deposited; this is in stark contrast to the films prepared by the conventional spin-casting technique. In spite of the seemingly unfavorable molecular orientations andmore » the highly disordered morphologies, the in-plane charge carrier transport characteristics of the MAPLE samples are comparable to those of spin-cast samples, exhibiting similar transport activation energies (56 meV versus 54 meV) to those reported in the literature for high mobility polymers.« less

  7. Subgap Absorption in Conjugated Polymers

    DOE R&D Accomplishments Database

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

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

    PubMed

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

    2015-02-11

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

  9. Solvent Polarity Effect on Chain Conformation, Film Morphology, and Optical Properties of a Water-Soluble Conjugated Polymer

    SciTech Connect

    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.

  10. Compositions for directed alignment of conjugated polymers

    DOEpatents

    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).

  11. Enhanced photophysics of conjugated polymers

    DOEpatents

    Chen, Liaohai; Xu, Su; McBranch, Duncan; Whitten, David

    2003-05-27

    The addition of oppositely charged surfactant to fluorescent ionic conjugated polymer forms a polymer-surfactant complex that exhibits at least one improved photophysical property. The conjugated polymer is a fluorescent ionic polymer that typically has at least one ionic side chain or moiety that interacts with the specific surfactant selected. The photophysical property improvements may include increased fluorescence quantum efficiency, wavelength-independent emission and absorption spectra, and more stable fluorescence decay kinetics. The complexation typically occurs in a solution of a polar solvent in which the polymer and surfactant are soluble, but it may also occur in a mixture of solvents. The solution is commonly prepared with a surfactant molecule:monomer repeat unit of polymer ratio ranging from about 1:100 to about 1:1. A polymer-surfactant complex precipitate is formed as the ratio approaches 1:1. This precipitate is recoverable and usable in many forms.

  12. Impact of Resonant Infrared Matrix-Assisted Pulsed Laser Evaporation (RIR-MAPLE) on Morphology and Charge Conduction in Conjugated Polymer and Bulk Heterojunction Thin Films

    NASA Astrophysics Data System (ADS)

    Stiff-Roberts, Adrienne; McCormick, Ryan; Atewologun, Ayomide

    2014-03-01

    An approach to improve organic photovoltaic efficiency is to increase vertical charge conduction by promoting out-of-plane π- π stacking in conjugated polymers. Resonant infrared matrix-assisted pulsed laser evaporation (RIR-MAPLE) features multiple growth parameters that can be varied to achieve a desired organic thin film property. In addition, RIR-MAPLE enables nanoscale domains in blended polymeric films and multi-layer polymeric films regardless of constituent solubility. Thus, RIR-MAPLE deposition is compared to solution-cast films as a possible approach to increase out-of-plane charge transport in polymers and bulk heterojunctions. Two common, solar cell polymers are investigated: P3HT and PCPDTBT. Materials characterization includes grazing-incidence, wide angle x-ray scattering (GIWAXS) for structural information and two techniques to determine hole mobility: organic field effect transistors to measure in-plane mobility and charge extraction by linearly increasing voltage to measure out-of-plane mobility. Initial indications are that the RIR-MAPLE films have a fundamentally different morphology compared to solution-cast films. In the case of P3HT, an enhancement in out-of-plane π- π stacking was observed by GIWAXS in RIR-MAPLE films compared to solution-cast films. A portion of this research was conducted at CNMS at ORNL.

  13. Enhanced photophysics of conjugated polymers

    DOEpatents

    Chen, Liaohai

    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.

  14. Local Electronic Characterization of Conjugated Polymer Films using Conducting-Probe Atomic Force Microscopy

    NASA Astrophysics Data System (ADS)

    O'Brien, G.; Quinn, A. J.; Redmond, G.

    2004-03-01

    Correlation of local electronic properties with film morphology is a key challenge to be addressed in order to understand (and therefore control) charge injection, transport and recombination in organic electronic devices. We present a flexible method, Conducting-Probe Atomic Force Microscopy (CP-AFM), which can be used as a local probe of both film morphology and spectroscopy. MEH-PPV layers with thickness values comparable to films used in organic electronic devices (60 nm) are spun onto gold substrates under inert conditions. Tip-height vs bias voltage (z-V) sweeps taken at constant tunnel current (50 pA) show clear charge injection thresholds at both positive and negative bias (E_+,E_-). Statistical analysis of measured single-particle gap energies, E_gsp=E_+-E_-, reveals a distribution across the surface with peaks corresponding to (extracted) exciton binding energies of 100 meV and 400 meV respectively. Analysis of measured E_gsp values for films prepared under ambient conditions show a large density of mid-gap states confirming that the preparation route is critical for organic electronic devices.

  15. Nanostructured conjugated polymers for photovoltaic devices

    NASA Astrophysics Data System (ADS)

    Xi, Dongjuan

    This dissertation focuses on making new systems of interdigitated bilayer structures for organic solar cells from two aspects: (i) fabricating vertically aligned semiconductor nanorod arrays by low-temperature solution process; (ii) applying the resulting nanorods arrays in solar cell devices with pre-formed or in-situ electropolymerized conjugated polymers. Two low-temperature solution methods are investigated to fabricate vertically aligned semiconductor nanorod arrays. The first method is using porous templates to prepare vertically aligned conjugated polymer nanorods arrays. In-situ anodized nanoporous alumina film is specifically designed to suspend on substrates to improve the wettability of organic solution to the alumina film, and to generate a big foot anchoring the polymer nanorods. With this specific design, vertically aligned polymer nanotube arrays with high density, 3x1010/cm2, is achieved and the nanotubes can stand vertically at the aspect ratio of 5. The second method is low-temperature direct growth of high quality semiconductor nanorod arrays without any templates by electrochemical deposition. Vertically aligned cadmium sulfide nanorod arrays are achieved by studying the growth mechanism of cadmium sulfide nanocrystal deposition and fine tuning the solution composition of the electrolyte. Chlorine doping, as a function of chlorine ion concentration in the electrolyte, modifies crystal lattice, and therefore the build-in stress, which dominates the morphology of the deposited nanocrystals as nanorods or thin films. Scanning electron microscopy, x-ray diffraction and transmission electron microscopy are applied to study the microstructures of the nanorods. Optical, electrical and field emission properties of the cadmium sulfide nanorod arrays are also studied in detail to pursue further applications of the nanorod arrays as nano-lasers and cold field emitters. Organic solar cells based on template-processed polythiophene nanotube arrays will be

  16. Conjugated Polymer Solar Cells

    DTIC Science & Technology

    2006-05-01

    MEH-PPV films prepared by drop- casting and slow solvent elimination (SSE) methods from chlorobenzene, toluene, and cyclohexanone solutions...After analysis of the literature data, we selected the following solvents for MEH-PPV: • Chlorobenzene, • Toluene, • Cyclohexanone . The...is seen that cyclohexanone results in a smoother optical absorption edge and a broader PL spectrum. These features are commonly attributed to a

  17. High Mobility Conjugated Polymers

    DTIC Science & Technology

    2007-10-20

    A schematic of the all-polymer inverter is shown Fig. 6 (c). Gold source and drain electrodes were patterned on a heavily doped silicon substrate...luminance o - - characteristics of an ITO/ PEDOT /TAPC k D r a Vol gt, V, (V) /BPQ-PPO/LiF/A! device are shown in Fig. 30. (A) Current density-voltage...The device Io architecture of ITO/ PEDOT /PVKIBQPQ/TPBI/LiF/AI showed the wa m r best performance with a brightness of 16255 cd/n (Figure 9b). The

  18. Photoluminescence of Conjugated Star Polymers

    NASA Astrophysics Data System (ADS)

    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.

  19. Highly selective "turn-on" fluorescent sensing of fluoride ion based on a conjugated polymer thin film-Fe(3+) complex.

    PubMed

    Ding, Wanchuan; Xu, Jingkun; Wen, Yangping; Zhang, Jie; Liu, Hongtao; Zhang, Zhouxiang

    2017-05-15

    We designed a new fluorescent conjugated polymer thin film sensor via direct electropolymerization of the corresponding electroactive monomer M onto the surface of ITO electrode, and the thin film-Fe(3+) complex was used for the highly-selective detection of fluoride ion (F(-)) in water environmental samples. The as-obtained thin film could effectively detect Fe(3+) as a selective turn-off fluorescent sensor, and exhibited outstanding reversibility. This film in the presence of Fe(3+) showed a highly selective turn-on response toward F(-) over other anions with a 5-fold enhancement in the fluorescence intensity. F(-) with a relatively wide concentration range from 10 μM to 3 mM could be determined in a rather simple and sensitive manner with a detection limit of 6.78 μM (0.128 ppm). Analytical applicability of the film-Fe(3+) complex for determining the levels of F(-) in environmental water samples has been successfully demonstrated by fluorescent analysis with satisfactory results. This strategy will provide a new approach for the facile design of new molecular sensing devices and practical application in environments.

  20. Electronic thermal conductivity, thermoelectric properties and supercapacitive behaviour of conjugated polymer nanocomposite (polyaniline-WO3) thin film

    NASA Astrophysics Data System (ADS)

    Chinedu Amaechi, Ifeanyichukwu; Nwanya, Assumpta C.; Ekwealor, Azubike B. C.; Asogwa, Paul U.; Osuji, Rose U.; Maaza, Malik; Ezema, Fabian I.

    2015-03-01

    A facile two-step, binder-free, chemical bath deposition (CBD) method was successfully employed in the synthesis of WO3 nanograins onto the matrix of conjugated polymer (polyaniline). The X-ray diffraction (XRD) results showed that the nanocomposite retained monoclinic phase of WO3 even when dispersed in polyaniline matrix. Owing to the synergistic effect offered by both the nanocomposite and structured metal oxide which may enhance the surface area, polyaniline-WO3 nanocomposite exhibited good specific capacitance. Polyaniline-WO3 yielded maximum specific capacitance ~96 F/g at scan rate of 5 mV/s in 0.5 M H2SO4 electrolyte. With the electronic thermal conductivity showing strong dependence on temperature, the estimated dimensionless figure of merit zT ~ 10-3 shows that the polymer nanocomposite (PNC) is promising as a new type of thermoelectric material. The electrochemical impedance spectroscopy showed that the PNC exhibited both pseudocapacitive and electric double layer capacitance behaviour.

  1. Hybrid electronics and electrochemistry with conjugated polymers.

    PubMed

    Inganäs, Olle

    2010-07-01

    In this critical review, we discuss the history and development of polymer devices wherein manipulation of the electronic conductivity by electrochemical redox processes in a conjugated polymer is used to form new functions. The devices employed are an electrochemical transistor, an electrolyte-gated field-effect transistor and light-emitting electrochemical cells, all of which combine doping/undoping of a conjugated polymer with modification of electronic transport (130 references).

  2. Quantitative electrochemical and electrochromic behavior of terthiophene and carbazole containing conjugated polymer network film precursors: EC-QCM and EC-SPR.

    PubMed

    Taranekar, Prasad; Fulghum, Timothy; Baba, Akira; Patton, Derek; Advincula, Rigoberto

    2007-01-16

    A comparative analysis of the copolymerization behavior between an electro-active terthiophene and a carbazole moiety of a conjugated polymer precursor was investigated using electrochemical and hyphenated electrochemical methods. Five different precursor polymers were first synthesized and characterized using NMR, IR, and GPC. The polymers include homopolymers of individual electro-active groups (P3T, P-CBZ) and different compositions of 25, 50, and 75% (P3TC-25, P3TC50, and P3TC-75) with respect to the two electro-active groups. Since the oxidation potentials of terthiophene and carbazole lie very close to each other, highly cross-linked copolymer films of varying extent were produced depending on the composition. The copolymerization extent was found to be dependent primarily on the amount of the terthiophene, which in this case provided for a more efficient carbazole polymerization and copolymerization than with just carbazole alone (homopolymer). The extent of copolymerization, electrochromic properties, and viscoelastic changes was quantitatively investigated using a number of hyphenated electrochemistry techniques: spectro-electrochemistry, electrochemical quartz crystal microbalance studies (EC-QCM), and electrochemical surface plasmon resonance spectroscopy (EC-SPR). Each technique revealed a unique aspect of the electrocopolymerization behavior that was used to define structure-property relationships and the deposition/copolymerization mechanism.

  3. Near-field scanning optical microscopy investigations of conjugated polymers

    NASA Astrophysics Data System (ADS)

    Dearo, Jessie Ann

    The Near-Field Scanning Optical Microscopy (NSOM) studies of novel, optically active, conjugated polymers are presented. NSOM is a relatively new technique which produces super resolution (˜50--100 nm) optical images simultaneously with topography. The conjugated polymer poly(p-phenylene vinylene) (PPV) and derivatives of PPV are organic semiconductor-like materials with interesting and unique optical properties. Derivatives of PPV have been used in LEDs and have potential in other optoelectronic devices. NSOM provides a tool for investigation of the photoluminescence, absorption/reflection, photo-dynamics and photoconductivity of films of PPV and PPV derivatives on the length scale that these properties are fundamentally defined. The NSOM experiments have revealed mesoscale domains (˜100 nm) of varying photoluminescence emission and average molecular order in drop cast films of PPV. NSOM of stretch-oriented PPV have shown domains of perpendicular molecular orientation with low photoluminescence emission. Near-field photoconductivity experiments of stretch-oriented PPV have correlated the mesoscale topography with the photoconductivity properties of the polymer. NSOM experiments of films of poly(2-methoxy, 5-(2'-(ethyl(hexyloxy)-p-phenylene vinylene) (MEH-PPV) have shown that there is mesoscale spatial inhomogeneity in the photo-oxidation process which reduces photoluminescence emission. NSOM has also been used to create nanoscale photo-patterning in MEH-PPV films. The NSOM experiments of blended films of MEH-PPV in polystyrene have shown mesoscale phase separation directly correlated to variations in the optical properties of the film. Derivatives of PPV, stretch-oriented in polyethylene, show photoluminescence intensity variations perpendicular and parallel to the stretch-direction correlated to topography features. As a complement to the NSOM studies of conjugated polymers, single polymer molecule experiments of MEH-PPV are also presented. The

  4. Microfluidic Crystal Engineering of π-Conjugated Polymers.

    PubMed

    Wang, Gang; Persson, Nils; Chu, Ping-Hsun; Kleinhenz, Nabil; Fu, Boyi; Chang, Mincheol; Deb, Nabankur; Mao, Yimin; Wang, Hongzhi; Grover, Martha A; Reichmanis, Elsa

    2015-08-25

    Very few studies have reported oriented crystallization of conjugated polymers directly in solution. Here, solution crystallization of conjugated polymers in a microfluidic system is found to produce tightly π-stacked fibers with commensurate improved charge transport characteristics. For poly(3-hexylthiophene) (P3HT) films, processing under flow caused exciton bandwidth to decrease from 140 to 25 meV, π-π stacking distance to decrease from 3.93 to 3.72 Å and hole mobility to increase from an average of 0.013 to 0.16 cm(2) V(-1) s(-1), vs films spin-coated from pristine, untreated solutions. Variation of the flow rate affected thin-film structure and properties, with an intermediate flow rate of 0.25 m s(-1) yielding the optimal π-π stacking distance and mobility. The flow process included sequential cooling followed by low-dose ultraviolet irradiation that promoted growth of conjugated polymer fibers. Image analysis coupled with mechanistic interpretation supports the supposition that "tie chains" provide for charge transport pathways between nanoaggregated structures. The "microfluidic flow enhanced semiconducting polymer crystal engineering" was also successfully applied to a representative electron transport polymer and a nonhalogenated solvent. The process can be applied as a general strategy and is expected to facilitate the fabrication of high-performance electrically active polymer devices.

  5. Surface directed assembly of conjugated polymers for optoelectronics

    NASA Astrophysics Data System (ADS)

    Liang, Ziqi

    Conjugated polymers combining the optical and electronic properties of semiconductors with advantages of organic materials are being explored as active components in various types of thin-film electronic and optoelectronic devices. The realization of conjugated polymer based electronics and optoelectronics critically depends on developing novel approaches for assembling this new class of materials into a controlled fashion. We have developed new non-photolithographic methods for the spatial deposition of conjugated polymers. As a proof-of-concept of these methods, the well-known luminescent polymer, poly(p-phenylene vinylene) (PPV), has been used as a model structure in our work. One strategy is based on the modification of solid substrates with microcontact-printed self-assembled monolayers (SAMs) that serve as templates for the deposition of PPVs from solution. Conjugated polymer patterns have also been generated by directly stamping of PPVs onto the reactive SAMs-coated substrates. In both methods, PPVs were covalently immobilized onto the supporting surface through the formation of amide bonds, thus rendering great stability of the resulting patterns. Well-defined PPV micropatterns have been fully characterized by UV-vis spectroscopy, atomic force microscopy (AFM), scanning electron microscopy (SEM) and fluorescence optical microscopy. The interaction between PPVs and the underlying surface was analyzed by grazing-angle reflectance Fourier transform infrared (FTIR) spectroscopy and X-ray photoelectron spectroscopy (XPS). Many applications based on conjugated polymers require the controlled assembly of the polymers as multilayer structures, in which molecules with different functionality can be incorporated into individual layers with precisely controlled thickness. We have developed a series of layer-by-layer (LbL) assembly approaches to multilayer conjugated polymer thin films. Hydrogen-bonding interaction and covalent coupling reaction have been utilized

  6. Conjugated amplifying polymers for optical sensing applications.

    PubMed

    Rochat, Sébastien; Swager, Timothy M

    2013-06-12

    Thanks to their unique optical and electrochemical properties, conjugated polymers have attracted considerable attention over the last two decades and resulted in numerous technological innovations. In particular, their implementation in sensing schemes and devices was widely investigated and produced a multitude of sensory systems and transduction mechanisms. Conjugated polymers possess numerous attractive features that make them particularly suitable for a broad variety of sensing tasks. They display sensory signal amplification (compared to their small-molecule counterparts) and their structures can easily be tailored to adjust solubility, absorption/emission wavelengths, energy offsets for excited state electron transfer, and/or for use in solution or in the solid state. This versatility has made conjugated polymers a fluorescence sensory platform of choice in the recent years. In this review, we highlight a variety of conjugated polymer-based sensory mechanisms together with selected examples from the recent literature.

  7. Conjugation Length Distribution in Poly(p-phenylenevinylene) (PPV) Films.

    PubMed

    da Silva, Marcelo C; Cassemiro, Sandra de M; Machado, Angelita M; Alves, Joniel C F; Nogueira, Sandra L; Jarrosson, Thibault; Serein-Spirau, Françoise; Akcelrud, Leni; Tozoni, José R; Silva, Raigna A; Freire, José A; Marletta, Alexandre

    2016-12-15

    We studied the absorption line-shape of poly(p-phenylenevinylene) (PPV) films deposited via spin coating and Langmuir-Blodgett techniques with the intent of identifying the conjugation length distribution in these two types of films, a key morphological aspect of conjugated polymer films. We treated the excitons in the polymer as independent oligomer excitons and modeled the absorption spectra of the individual oligomers using simple expressions for the oligomer size dependence of the gap energy, the line-broadening factor, the transition dipole moment and the Huang-Rhys parameter. We validated these expressions by independent measurements on phenyl-based oligomers and Density Functional Theory calculations. Our results show clear evidence that, for both types of PPV films, the conjugation length distribution depends exponentially on the segment size. Our results also set a lower limit, of about ten repeat units, for the maximum exciton length of three different phenyl-based oligomers.

  8. High-Performing Thin-Film Transistors in Large Spherulites of Conjugated Polymer Formed by Epitaxial Growth on Removable Organic Crystalline Templates.

    PubMed

    Kim, Jae Yoon; Yang, Da Seul; Shin, Jicheol; Bilby, David; Chung, Kyeongwoon; Um, Hyun Ah; Chun, Jaehee; Pyo, Seungmoon; Cho, Min Ju; Kim, Jinsang; Choi, Dong Hoon

    2015-06-24

    Diketopyrrolopyrrole (DPP)-based conjugated polymer PDTDPPQT was synthesized and was used to perform epitaxial polymer crystal growth on removable 1,3,5-trichlorobenzene crystallite templates. A thin-film transistor (TFT) was successfully fabricated in well-grown large spherulites of PDTDPPQT. The charge carrier mobility along the radial direction of the spherulites was measured to be 5.46-12.04 cm(2) V(-1) s(-1), which is significantly higher than that in the direction perpendicular to the radial direction. The dynamic response of charge transport was also investigated by applying a pulsed bias to TFTs loaded with a resistor (∼20 MΩ). The charge-transport behaviors along the radial direction and perpendicular to the radial direction were investigated by static and dynamic experiments through a resistor-loaded (RL) inverter. The RL inverter made of PDTDPPQT-based TFT operates well, maintaining a fairly high switching voltage ratio (Vout(ON)/Vout(OFF)) at a relatively high frequency when the source-drain electrodes are aligned parallel to the radial direction.

  9. Compatibilization of All-Conjugated Polymer Blends for Organic Photovoltaics.

    PubMed

    Lombeck, Florian; Sepe, Alessandro; Thomann, Ralf; Friend, Richard H; Sommer, Michael

    2016-08-23

    Compatibilization of an immiscible binary blend comprising a conjugated electron donor and a conjugated electron acceptor polymer with suitable electronic properties upon addition of a block copolymer (BCP) composed of the same building blocks is demonstrated. Efficient compatibilization during melt-annealing is feasible when the two polymers are immiscible in the melt, i.e. above the melting point of ∼250 °C of the semicrystalline donor polymer P3HT. To generate immiscibility at these high temperatures, the acceptor polymer PCDTBT is equipped with fluorinated side chains leading to an increased Flory-Huggins interaction parameter. Compatibilization in bulk and thin films is demonstrated, showing that the photovoltaic performance of pristine microphase separated and nanostructured BCPs can also be obtained for compatibilized blend films containing low contents of 10-20 wt % BCP. Thermodynamically stable domain sizes range between several tens of microns for pure blends and ∼10 nm for pure block copolymers. In addition to controlling domain size, the amount of block copolymer added dictates the ratio of edge-on and face-on P3HT crystals, with compatibilized films showing an increasing amount of face-on P3HT crystals with increasing amount of compatibilizer. This study demonstrates the prerequisites and benefits of compatibilizing all-conjugated semicrystalline polymer blends for organic photovoltaics.

  10. Spectroscopy on Conjugated Polymer Devices

    NASA Astrophysics Data System (ADS)

    Dyakonov, Vladimir

    The following sections are included: * INTRODUCTION * EXPERIMENTAL * Sample Preparation * Experimental Set-up * Frequency Resolved ODMR * RESULTS * Studies on the Recombination and Transport in the Polymer Devices via Measurements of the Photoinduced Current and the Electroluminescence * ESR Detected via Photoinduced Current * Magnetic Field Effect on the Photocurrent * ESR Detected via Electroluminescence Intensity * Photoluminescence Studies on Films of PPV and PPPV * Changes of the Photoluminescence Intensity under Conditions of ESR * Dependence of the ODMR on the Excitation Intensity and the Temperature * Spectral Dependence of ODMR * Studies of the recombination kinetics by means of frequency resolved ODMR * The Influence of the Thermal Conversion of PPV on the ODMR Intensity * DISCUSSION * On the Nature of the States Participating in Photocurrent Detected Magnetic Resonance * Excitations Participating in Electroluminescence Detected Magnetic Resonance * Evidences for Photoinduced Inter-Chain Triplet Polaron Pairs and Their Transformations In PPV * Triplet Excitons Annihilation as Origin of the Delayed Photoluminescence * Kinetic Connection Between Magnetic Resonant Transitions and Photo-Luminescence Intensity * Dependence of the Magnitude of the Resonant Signals on the Light Intensity * Dependence of the Magnitude of the Resonant Signals on the Frequency of Microwave Power Modulation * On the Polarisation of Triplet Excitons * Temperature Dependence of the ODMR Intensity * The Influence of the Thermal Conversion of the Prepolymer on Recombination Processes * Remarks on the Previous Recombination Models in Magnetic Resonance Experiments * CONCLUSION * Acknowledgements * REFERENCES

  11. Direct probing of a polymer electrolyte/luminescent conjugated polymer mixed ionic/electronic conductor.

    PubMed

    Hu, Yufeng; Gao, Jun

    2009-12-30

    What will happen if one brings two metallic probes into direct contact with a polymer film and apply a voltage bias? We demonstrate that, for a mixed ionic/electronic conductor containing a luminescent conjugated polymer and a polymer electrolyte, it is possible to induce strong in situ electrochemical doping of the luminescent polymer and form a dynamic light-emitting p-n junction. Using time-lapse fluorescence imaging, we have visualized p- and n-doping of various shapes and shades, p-n junction electroluminescence, and the effects of voltage reversal. The direct probing technique offers great simplicity and versatility for studying luminescent mixed ionic/electronic conductors.

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

    NASA Astrophysics Data System (ADS)

    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

  13. Conjugated polymer networks: Synthesis and properties

    NASA Astrophysics Data System (ADS)

    Kokil, Akshay

    The experimental research program that forms the basis of this thesis has been directed towards the design, synthesis, processing and physical characterization of well-defined conjugated polymer networks. It attempts to provide answers to the questions how such materials can be synthesized and processed and how the introduction of cross-links can be exploited for the creation of polymeric materials with optimized optic and electronic characteristics. Interestingly, this family of materials has received little attention in the past, at least as far as systematic studies of well-defined systems are concerned. This situation may be a direct consequence of the challenge to introduce conjugated cross-links into conjugated polymers and retain adequate processibility. We have shown that organometallic polymer networks based on linear conjugated polymers are readily accessible through ligand-exchange reactions. This approach was exemplified by exploiting the ethynyl moieties comprised in poly( p-phenylene ethynylene) (PPE) derivatives as ligand sites, which allow for complexation with selected metals and cross-linking via the resulting PPE-Metal complexes. Focusing on the dinuclear complex [Pt-(mu-Cl)Cl-PPE] 2 and PPE-Pt0 as crosslinks, we have conducted an in-depth investigation on how the nature of the metal cross-links influences the materials characteristics, in particular the charge transport properties. We first investigated the charge carrier mobility of poly[2,5-dioctyloxy-1,4-diethynyl-phenylene- alt-2,5-bis(2'-ethylhexyloxy)-1,4-phenylene] (EHO-OPPE), as a classic representative of poly(p-phenylene ethynylene) (PPE) derivatives, which represent an important class of conjugated polymers. In what appears to be the first study ever conducted on the mobility of any PPE, we found that EHO-OPPE displays ambipolar charge transport characteristics with very high electron (1.9·10-3 cm2V-1 s-1) and hole (1.6·10-3 cm 2V-1s-1) mobilities. Most importantly, the introduction

  14. Band bending in conjugated polymer layers.

    PubMed

    Lange, Ilja; Blakesley, James C; Frisch, Johannes; Vollmer, Antje; Koch, Norbert; Neher, Dieter

    2011-05-27

    We use the Kelvin probe method to study the energy-level alignment of four conjugated polymers deposited on various electrodes. Band bending is observed in all polymers when the substrate work function exceeds critical values. Through modeling, we show that the band bending is explained by charge transfer from the electrodes into a small density of states that extends several hundred meV into the band gap. The energetic spread of these states is correlated with charge-carrier mobilities, suggesting that the same states also govern charge transport in the bulk of these polymers.

  15. Ultrafast Relaxation in Conjugated Polymers

    NASA Astrophysics Data System (ADS)

    Kobayashi, Takayoshi

    The following sections are included: * INTRODUCTION * EXPERIMENTAL * Samples * Femtosecond experimental apparatus * RESULTS AND DISCUSSION * Poly(phenylacetylenes) * Blue-phase PDA-3BCMU * Red-phase PDA-4BCMU * Blue-phase PDA-DFMP * P3MT * P3DT * PTV * RELAXATION MECHANISMS * Review of the previous works * Symmetry of the lower electronic excited states * Primary relaxation processes * Theoretical studies of nonlinear excitations * Mechanism of relaxation in polymers with a weakly nondegenerate ground state (poly(phenylacetylene)s) * Dual peak component with power-law decay * Single-peak component with an exponential decay * Hot self-trapped exciton * Transition to the electron-hole threshold * Transition to a biexciton state * Mechanism of relaxation in polymers with a strongly or moderately nondegenerate ground state * Classifications of polymers * Femtosecond relaxation * Picosecond relaxation * CONCLUSION * Acknowledgments * REFERENCES

  16. Conjugated Polymers Atypically Prepared in Water

    PubMed Central

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

    2010-01-01

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

  17. Solvent immersion nanoimprint lithography of fluorescent conjugated polymers

    NASA Astrophysics Data System (ADS)

    Whitworth, G. L.; Zhang, S.; Stevenson, J. R. Y.; Ebenhoch, B.; Samuel, I. D. W.; Turnbull, G. A.

    2015-10-01

    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/cm2, 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.

  18. Crosslinked polymer nanoparticles containing single conjugated polymer chains.

    PubMed

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

    2017-03-29

    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.

  19. Photoluminescence quenching of conjugated polymer nanocomposites for gamma ray detection

    NASA Astrophysics Data System (ADS)

    Zhong, Haizheng; Zhao, Yong Sheng; Li, Yongfang; Pei, Qibing

    2008-12-01

    The high atomic number of bismuth iodide and the high-sensitivity photoluminescence quenching of conjugated polymers are leveraged in their nanocomposites for the detection of high-energy photons. With the introduction of oleylamine, the composites can be processed from solutions in organic solvent into high-quality films containing as much as 50 wt% BiI3. BiI3 in the resulting ternary composites is dispersed on a nanoscale or smaller, allowing the formation of transparent composites. Oleylamine was found to form an interfacial layer between the polymer matrix and BiI3 nanodomains to block charge transfer between BiI3 and the polymer. Upon gamma ray exposure, the luminescent intensity of the ternary composites decreased linearly with the radiation dosage.

  20. Highly Sensitive Thin-Film Field-Effect Transistor Sensor for Ammonia with the DPP-Bithiophene Conjugated Polymer Entailing Thermally Cleavable tert-Butoxy Groups in the Side Chains.

    PubMed

    Yang, Yang; Zhang, Guanxin; Luo, Hewei; Yao, Jingjing; Liu, Zitong; Zhang, Deqing

    2016-02-17

    The sensing and detection of ammonia have received increasing attention in recent years because of the growing emphasis on environmental and health issues. In this paper, we report a thin-film field-effect transistor (FET)-based sensor for ammonia and other amines with remarkable high sensitivity and satisfactory selectivity by employing the DPP-bithiophene conjugated polymer pDPPBu-BT in which tert-butoxycarboxyl groups are incorporated in the side chains. This polymer thin film shows p-type semiconducting property. On the basis of TGA and FT-IR analysis, tert-butoxycarboxyl groups can be transformed into the -COOH ones by eliminating gaseous isobutylene after thermal annealing of pDPPBu-BT thin film at 240 °C. The FET with the thermally treated thin film of pDPPBu-BT displays remarkably sensitive and selective response toward ammonia and volatile amines. This can be attributed to the fact that the elimination of gaseous isobutylene accompanies the formation of nanopores with the thin film, which will facilitate the diffusion and interaction of ammonia and other amines with the semiconducting layer, leading to high sensitivity and fast response for this FET sensor. This FET sensor can detect ammonia down to 10 ppb and the interferences from other volatile analytes except amines can be negligible.

  1. Electronic properties of sulfur containing conjugated polymers

    NASA Astrophysics Data System (ADS)

    Brédas, J. L.; Elsenbaumer, R. L.; Chance, R. R.; Silbey, Robert

    1983-05-01

    Valence effective Hamiltonian (VEH) calculations are performed on a number of sulfur containing organic conjugated polymers of interest to the conducting polymers area. Theoretical results for parameters related to conductivity such as ionization potentials, bandwidths, and bandgaps are presented. Systems considered include various derivatives of poly (p-phenylene sulfide), polybenzothiophene, and polythiophene, as well as potentially interesting compounds such as polythieno [3,2-b] thiophene and polyvinylene sulfide. The electronic structure description afforded by the VEH method for sulfur containing polymers is demonstrated to be of the same quality as that presented previously for hydrocarbon polymers. In particular, for ionization potentials, good agreement with available experimental data on poly (p-phenylene sulfide) and polybenzothiophene is obtained, after scaling downward the VEH values by a 1.9 eV polarization correction. The comparison between the theoretical and experimental XPS spectra for polybenzothiophene is excellent with use of the same energy scaling factor previously employed for polyacetylene, poly(p-phenylene), and poly(p-phenylene sulfide). These results, in conjuction with previous results obtained on hydrocarbon polymers, lend confidence in the predictive capabilities of this purely theoretical technique. Calculations show that polyvinylene sulfide, as yet unsynthesized, should display very promising characteristics as a conducting polymer.

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

    PubMed

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

    SciTech Connect

    Chen, Wu

    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.

  4. Antistaphylococcal Nanocomposite Films Based on Enzyme-Nanotube Conjugates

    PubMed Central

    Pangule, Ravindra C.; Brooks, Sarah J.; Dinu, Cerasela Zoica; Bale, Shyam Sundhar; Salmon, Sharon L.; Zhu, Guangyu; Metzger, Dennis W.; Kane, Ravi S.; Dordick, Jonathan S.

    2010-01-01

    Infection with antibiotic-resistant pathogens such as methicillin-resistant Staphylococcus aureus (MRSA) is one of the primary causes of hospitalizations and deaths. To address this issue, we have designed antimicrobial coatings incorporating carbon nanotube-enzyme conjugates that are highly effective against antibiotic–resistant pathogens. Specifically, we incorporated conjugates of carbon nanotubes with lysostaphin, a cell wall degrading enzyme, into films to impart bactericidal properties against Staphylococcus aureus and Staphylococcus epidermidis. We fabricated and characterized nanocomposites containing different conjugate formulations and enzyme loadings. These enzyme–based composites were highly efficient in killing MRSA (>99% within 2 h) without release of the enzyme into solution. Additionally, these films were reusable and stable under dry storage conditions for a month. Such enzyme–based film formulations may be used to prevent growth of pathogenic and antibiotic-resistant microorganisms on various common surfaces in hospital settings. Polymer and paint films containing such antimicrobial conjugates, in particular, could be advantageous to prevent risk of staphylococcal-specific infection and biofouling. PMID:20604574

  5. A molecular design principle of lyotropic liquid-crystalline conjugated polymers with directed alignment capability for plastic electronics.

    PubMed

    Kim, Bong-Gi; Jeong, Eun Jeong; Chung, Jong Won; Seo, Sungbaek; Koo, Bonwon; Kim, Jinsang

    2013-07-01

    Conjugated polymers with a one-dimensional p-orbital overlap exhibit optoelectronic anisotropy. Their unique anisotropic properties can be fully realized in device applications only when the conjugated chains are aligned. Here, we report a molecular design principle of conjugated polymers to achieve concentration-regulated chain planarization, self-assembly, liquid-crystal-like good mobility and non-interdigitated side chains. As a consequence of these intra- and intermolecular attributes, chain alignment along an applied flow field occurs. This liquid-crystalline conjugated polymer was realized by incorporating intramolecular sulphur-fluorine interactions and bulky side chains linked to a tetrahedral carbon having a large form factor. By optimizing the polymer concentration and the flow field, we could achieve a high dichroic ratio of 16.67 in emission from conducting conjugated polymer films. Two-dimensional grazing-incidence X-ray diffraction was performed to analyse a well-defined conjugated polymer alignment. Thin-film transistors built on highly aligned conjugated polymer films showed more than three orders of magnitude faster carrier mobility along the conjugated polymer alignment direction than the perpendicular direction.

  6. Responsive Guest Encapsulation of Dynamic Conjugated Microporous Polymers.

    PubMed

    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.

  7. Responsive Guest Encapsulation of Dynamic Conjugated Microporous Polymers

    PubMed Central

    Xu, Lai; Li, Youyong

    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 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. PMID:27356483

  8. Conjugated polymer sensors built on pi-extended borasiloxane cages.

    PubMed

    Liu, Wenjun; Pink, Maren; Lee, Dongwhan

    2009-06-24

    An efficient 2 + 2 cyclocondensation with dihydroxysilane converted simple arylboronic acids to bifunctional borasiloxane cage molecules, which were subsequently electropolymerized to furnish air-stable thin films. The extended [p,pi]-conjugation that defines the rigid backbone of this new conjugated polymer (CP) motif gives rise to longer-wavelength UV-vis transitions upon oxidative doping, the spectral window and intensity of which can be modified by interaction with Lewis basic reagents. Notably, this boron-containing CP undergoes a rapid and reversible color change from green to orange upon exposure to volatile amine samples under ambient conditions. This direct naked-eye detection scheme can best be explained by invoking the reversible B-N dative bond formation that profoundly influences the p-pi* orbital overlap.

  9. Overcoming Film Quality Issues for Conjugated Polymers Doped with F4TCNQ by Solution Sequential Processing: Hall Effect, Structural, and Optical Measurements.

    PubMed

    Scholes, D Tyler; Hawks, Steven A; Yee, Patrick Y; Wu, Hao; Lindemuth, Jeffrey R; Tolbert, Sarah H; Schwartz, Benjamin J

    2015-12-03

    We demonstrate that solution-sequential processing (SqP) can yield heavily doped pristine-quality films when used to infiltrate the molecular dopant 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F4TCNQ) into pure poly(3-hexylthiophene) (P3HT) polymer layers. Profilometry measurements show that the SqP method produces doped films with essentially the same surface roughness as pristine films, and 2-D grazing-incidence wide-angle X-ray scattering (GIWAXS) confirms that SqP preserves both the size and orientation of the pristine polymer's crystallites. Unlike traditional blend-cast F4TCNQ/P3HT doped films, our sequentially processed layers have tunable and reproducible conductivities reaching as high as 5.5 S/cm even when measured over macroscopic (>1 cm) distances. The high conductivity and superb film quality allow for meaningful Hall effect measurements, which reveal p-type conduction and carrier concentrations tunable from 10(16) to 10(20) cm(-3) and hole mobilities ranging from ∼0.003 to 0.02 cm(2) V(-1) s(-1) at room temperature over the doping levels examined.

  10. Oxygen-dependent hologram writing and fixing in conjugated polymer storage media

    NASA Astrophysics Data System (ADS)

    Levi, Ofer; Agranat, Aharon J.; Perepelitsa, Galina; Shalom, Shoshy; Neumann, Ronny; Avny, Yair; Davidov, Dan

    1999-11-01

    Hologram writing and fixing mechanisms are examined in disordered conjugated polymer/glass composites. The conjugated polymers used were alkoxy substituted poly(phenylenevinylne) analogs and the glass matrices were zirconia-organosilica xerogels. Hologram formation mechanism is shown to be a photochromic process consisting of light induced photo- oxidation (bleaching) of the embedded conjugated polymer resulting in the formation of an absorption grating and a phase grating. IR and Raman spectroscopy show that the chemical transformations upon photo-bleaching involve chain scission and oxidation of the polymer at the vinylic position of the conjugated polymer. Oxygen removal increases hologram formation time by more than an order of magnitude and halves the total hologram efficiency. The oxygen dependence was also highly correlated with photo-bleaching of the samples and beam interaction of the writing beams. Light sensitivity was compared for several polymer/glass composites showing that the new composites and film preparation techniques are promising for blue and ultraviolet sensitive holographic materials. A hologram fixing method based on a PMMA coating, applied on the film after hologram formation is demonstrated and shown to increase hologram erasure times by four. These important findings show that conjugated polymer/glass composites based storage media can be manufactured and fixed efficiently for a long term based on this method.

  11. Characterization of Nanostructured Polymer Films

    DTIC Science & Technology

    2014-12-23

    of the film for complete polymer chain relaxation, including relaxation of surface features . The presence of intact surface globules at a substrate...AFRL-OSR-VA-TR-2015-0059 Characterization of Nanostructured Polymer Films RODNEY PRIESTLEY TRUSTEES OF PRINCETON UNIVERSITY Final Report 12/23/2014...Report 3. DATES COVERED (From - To) 06/01/2012-08/31/2014 4. TITLE AND SUBTITLE Characterization of Nanostructured Polymer Films 5a. CONTRACT

  12. Controlling Molecular Ordering in Solution-State Conjugated Polymers

    SciTech Connect

    Zhu, Jiahua; Han, Youngkyu; Kumar, Rajeev; Hong, Kunlun; Bonnesen, Peter V.; Sumpter, Bobby G.; Smith, Gregory Scott; Ivanov, Ilia N.; Do, Changwoo

    2015-07-17

    Rationally encoding molecular interactions that can control the assembly structure and functional expression in solution of conjugated polymers holds great potential for enabling optimal organic optoelectronic and sensory materials. In this work, we show that thermally-controlled and surfactant-guided assembly of water-soluble conjugated polymers in aqueous solution is a simple and effective strategy to generate optoelectronic materials with desired molecular ordering. We have studied a conjugated polymer consisting of a hydrophobic thiophene backbone and hydrophilic, thermo-responsive ethylene oxide side groups, which shows a step-wise, multi-dimensional assembly in water. By incorporating the polymer into phase-segregated domains of an amphiphilic surfactant in solution, we demonstrate that both chain conformation and degree of molecular ordering of the conjugated polymer can be tuned in hexagonal, micellar and lamellar phases of the surfactant solution. The controlled molecular ordering in conjugated polymer assembly is demonstrated as a key factor determining the electronic interaction and optical function.

  13. Fluoro-Substituted n-Type Conjugated Polymers for Additive-Free All-Polymer Bulk Heterojunction Solar Cells with High Power Conversion Efficiency of 6.71.

    PubMed

    Jung, Jae Woong; Jo, Jea Woong; Chueh, Chu-Chen; Liu, Feng; Jo, Won Ho; Russell, Thomas P; Jen, Alex K-Y

    2015-06-03

    Fluorinated n-type conjugated polymers are used as efficient electron acceptor to demonstrate high-performance all-polymer solar cells. The exciton generation, dissociation, and charge-transporting properties of blend films are improved by using these fluorinated n-type polymers to result in enhanced photocurrent and suppressed charge recombination.

  14. Releasable Conjugation of Polymers to Proteins.

    PubMed

    Gong, Yuhui; Leroux, Jean-Christophe; Gauthier, Marc A

    2015-07-15

    Many synthetic strategies are available for preparing well-defined conjugates of peptides/proteins and polymers. Most reports on this topic involve coupling methoxy poly(ethylene glycol) to therapeutic proteins, a process referred to as PEGylation, to increase their circulation lifetime and reduce their immunogenicity. Unfortunately, the major dissuading dogma of PEGylation is that, in many cases, polymer modification leads to significant (or total) loss of activity/function. One approach that is gaining momentum to address this challenge is to release the native protein from the polymer with time in the body (releasable PEGylation). This contribution will present the state-of-the-art of this rapidly evolving field, with emphasis on the chemistry behind the release of the peptide/protein and the means for altering the rate of release in biological fluids. Linkers discussed include those based on the following: substituted maleic anhydride and succinates, disulfides, 1,6-benzyl-elimination, host-guest interactions, bicin, β-elimination, biodegradable polymers, E1cb elimination, β-alanine, photoimmolation, coordination chemistry, zymogen activation, proteolysis, and thioesters.

  15. Direct x-ray detection with conjugated polymer devices

    NASA Astrophysics Data System (ADS)

    Boroumand, F. A.; Zhu, M.; Dalton, A. B.; Keddie, J. L.; Sellin, P. J.; Gutierrez, J. J.

    2007-07-01

    The authors report the first direct detection of x-ray induced photocurrents in thick films (up to 20μm) of conjugated polymers. Schottky-based "sandwich" structures were fabricated from layers of either poly[1-methoxy-4-(2-ethylhexyloxy)-phenylenevinylene] (MEH-PPV) or poly(9,9-dioctylfluorene) (PFO) on indium tin oxide substrates using a top contact of aluminum. Good rectification was achieved from the Al-polymer contact, with a reverse bias leakage current density as low as 4nA/cm2 at an electric field strength of 25kV/cm. Irradiation with x-rays from a 50kV x-ray tube produced a linear increase in photocurrent over a dose rate range from 4to18mGy/s. The observed x-ray sensitivities of 240nC/mGy/cm3 for MEH-PPV and 480nC/mGy/cm3 for PFO structures are comparable to that reported for Si devices. A response time of <150ms to pulsed x-ray irradiation was measured with no evidence of long-lived current transients. Conjugated polymers offer the advantage of easy coatability over large areas and on curved surfaces. Their low average atomic number provides tissue-equivalent dosimetric response, with many potential applications including medical x-ray and synchrotron photon detection.

  16. Characterization of pi-Conjugated Polymers for Transistor and Photovoltaic Applications

    NASA Astrophysics Data System (ADS)

    Paulsen, Bryan D.

    pi-Conjugated polymers represent a unique class of optoelectronic materials. Being polymers, they are solution processable and inherently "soft" materials. This makes them attractive candidates for the production of roll-to-roll printed electronic devices on flexible substrates. The optical and electronic properties of pi-conjugated polymers are synthetically tunable allowing material sets to be tailored to specific applications. Two of the most heavily researched applications are the thin film transistor, the building block of electronic circuits, and the bulk heterojunction solar cell, which holds great potential as a renewable energy source. Key to developing commercially feasible pi-conjugated polymer devices is a thorough understanding of the electronic structure and charge transport behavior of these materials in relationship with polymer structure. Here this structure property relationship has been investigated through electrical and electrochemical means in concert with a variety of other characterization techniques and device test beds. The tunability of polymer optical band gap and frontier molecular orbital energy level was investigated in systems of vinyl incorporating statistical copolymers. Energy levels and band gaps are crucial parameters in developing efficient photovoltaic devices, with control of these parameters being highly desirable. Additionally, charge transport and density of electronic states were investigated in pi-conjugated polymers at extremely high electrochemically induced charge density. Finally, the effects of molecular weight on pi-conjugated polymer optical properties, energy levels, charge transport, morphology, and photovoltaic device performance was examined.

  17. Method for synthesizing peptides with saccharide linked enzyme polymer conjugates

    DOEpatents

    Callstrom, Matthew R.; Bednarski, Mark D.; Gruber, Patrick R.

    1997-01-01

    A method is disclosed for synthesizing peptides using water soluble enzyme polymer conjugates. The method comprises catalyzing the peptide synthesis with enzyme which has been covalently bonded to a polymer through at least three linkers which linkers have three or more hydroxyl groups. The enzyme is conjugated at lysines or arginines.

  18. Enzyme linked immunoassay with stabilized polymer saccharide enzyme conjugates

    DOEpatents

    Callstrom, Matthew R.; Bednarski, Mark D.; Gruber, Patrick R.

    1997-01-01

    An improvement in enzyme linked immunoassays is disclosed wherein the enzyme is in the form of a water soluble polymer saccharide conjugate which is stable in hostile environments. The conjugate comprises the enzyme which is linked to the polymer at multiple points through saccharide linker groups.

  19. Method for synthesizing peptides with saccharide linked enzyme polymer conjugates

    DOEpatents

    Callstrom, M.R.; Bednarski, M.D.; Gruber, P.R.

    1997-06-17

    A method is disclosed for synthesizing peptides using water soluble enzyme polymer conjugates. The method comprises catalyzing the peptide synthesis with enzyme which has been covalently bonded to a polymer through at least three linkers which linkers have three or more hydroxyl groups. The enzyme is conjugated at lysines or arginines. 19 figs.

  20. Enzyme linked immunoassay with stabilized polymer saccharide enzyme conjugates

    DOEpatents

    Callstrom, M.R.; Bednarski, M.D.; Gruber, P.R.

    1997-11-25

    An improvement in enzyme linked immunoassays is disclosed wherein the enzyme is in the form of a water soluble polymer saccharide conjugate which is stable in hostile environments. The conjugate comprises the enzyme which is linked to the polymer at multiple points through saccharide linker groups. 19 figs.

  1. Emerging Synthetic Techniques for Protein-Polymer Conjugations

    PubMed Central

    Broyer, Rebecca M.; Grover, Gregory N.; Maynard, Heather D.

    2011-01-01

    Protein-polymer conjugates are important in diverse fields including drug delivery, biotechnology, and nanotechnology. This feature article highlights recent advances in the synthesis and application of protein-polymer conjugates by controlled radical polymerization techniques. Special emphasis on new applications of the materials, particularly in biomedicine, are highlighted. PMID:21229146

  2. Conformational effects on excitation transport along conjugated polymer chains.

    PubMed

    Van Averbeke, Bernard; Beljonne, David

    2009-03-26

    The dynamics of energy transport along rigid rod conjugated polymer--poly(p-phenylenebutadyine)--chains is modeled with a special emphasis on the role of conformational disorder. A simple random growth algorithm based on torsion potentials with increasing stiffness yields polymer chains with increasing degree of conjugation and narrower energetic distributions. Despite the fact that the average hopping rate between two subunits is reduced (because the decrease in electronic coupling overwhelms the increase in spectral overlap), a more efficient excitation motion along chains with longer conjugated segments is predicted, in good agreement with recent experiments. This points to the central role of conformational disorder on intrachain energy diffusion in conjugated polymers.

  3. Thin films of photoactive polymer blends.

    PubMed

    Ruderer, Matthias A; Metwalli, Ezzeldin; Wang, Weinan; Kaune, Gunar; Roth, Stephan V; Müller-Buschbaum, Peter

    2009-03-09

    The morphology inside photoactive blended films of two conjugated homopolymers poly [(1-methoxy)-4-(2-ethylhexyloxy)-p-phenylene-vinylene] (MEH-PPV) and poly(3-hexylthiophene-2,5-diyl) (P3HT) is investigated. For both homopolymers a linear dependence of the installed film thickness from the concentration of the polymer solution used in spin coating is probed. This dependence allows preparation of an efficient series of blended films with constant thickness and different blending ratios. Information about the lateral structure inside the films is gained from grazing incidence small angle X-ray scattering. At the calculated critical blending ratio the smallest lateral separation between adjacent domains is found representing the highest surface contact between both homopolymers in the films. The presence of wetting layers at both interfaces as detected with X-ray reflectivity and atomic force microscopy is promising for photovoltaic applications. UV/Vis spectroscopy complements the structural investigation.

  4. Singlet fission of hot excitons in π-conjugated polymers.

    PubMed

    Zhai, Yaxin; Sheng, Chuanxiang; Vardeny, Z Valy

    2015-06-28

    We used steady-state photoinduced absorption (PA), excitation dependence (EXPA(ω)) spectrum of the triplet exciton PA band, and its magneto-PA (MPA(B)) response to investigate singlet fission (SF) of hot excitons into two separated triplet excitons, in two luminescent and non-luminescent π-conjugated polymers. From the high energy step in the triplet EXPA(ω) spectrum of the luminescent polymer poly(dioctyloxy)phenylenevinylene (DOO-PPV) films, we identified a hot-exciton SF (HE-SF) process having threshold energy at E≈2E(T) (=2.8 eV, where ET is the energy of the lowest lying triplet exciton), which is about 0.8 eV above the lowest singlet exciton energy. The HE-SF process was confirmed by the triplet MPA(B) response for excitation at E>2E(T), which shows typical SF response. This process is missing in DOO-PPV solution, showing that it is predominantly interchain in nature. By contrast, the triplet EXPA(ω) spectrum in the non-luminescent polymer polydiacetylene (PDA) is flat with an onset at E=E(g) (≈2.25 eV). From this, we infer that intrachain SF that involves a triplet-triplet pair state, also known as the 'dark' 2A(g) exciton, dominates the triplet photogeneration in PDA polymer as E(g)>2E(T). The intrachain SF process was also identified from the MPA(B) response of the triplet PA band in PDA. Our work shows that the SF process in π-conjugated polymers is a much more general process than thought previously.

  5. Dewetting of Thin Polymer Films

    NASA Astrophysics Data System (ADS)

    Dixit, P. S.; Sorensen, J. L.; Kent, M.; Jeon, H. S.

    2001-03-01

    DEWETTING OF THIN POLYMER FILMS P. S. Dixit,(1) J. L. Sorensen,(2) M. Kent,(2) H. S. Jeon*(1) (1) Department of Petroleum and Chemical Engineering, New Mexico Institute of Mining and Technology, 801 Leroy Place, Socorro, NM 87801, jeon@nmt.edu (2) Department 1832, Sandia National Laboratories, Albuquerque, NM. Dewetting of thin polymer films is of technological importance for a variety of applications such as protective coatings, dielectric layers, and adhesives. Stable and smooth films are required for the above applications. Above the glass transition temperature (Tg) the instability of polymer thin films on a nonwettable substrate can be occurred. The dewetting mechanism and structure of polypropylene (Tg = -20 ^circC) and polystyrene (Tg = 100 ^circC) thin films is investigated as a function of film thickness (25 Åh < 250 Åand quenching temperature. Contact angle measurements are used in conjunction with optical microscope to check the surface homogeneity of the films. Uniform thin films are prepared by spin casting the polymer solutions onto silicon substrates with different contact angles. We found that the stable and unstable regions of the thin films as a function of the film thickness and quenching temperature, and then constructed a stability diagram for the dewetting of thin polymer films. We also found that the dewetting patterns of the thin films are affected substantially by the changes of film thickness and quenching temperature.

  6. Scattering from Colloid-Polymer Conjugates with Excluded Volume Effect

    SciTech Connect

    Li, Xin; Sanchez-Diaz, Luis E.; Smith, Gregory Scott; Chen, Wei-Ren

    2015-01-13

    This work presents scattering functions of conjugates consisting of a colloid particle and a self-avoiding polymer chain as a model for protein-polymer conjugates and nanoparticle-polymer conjugates in solution. The model is directly derived from the two-point correlation function with the inclusion of excluded volume effects. The dependence of the calculated scattering function on the geometric shape of the colloid and polymer stiffness is investigated. The model is able to describe the experimental scattering signature of the solutions of suspending hard particle-polymer conjugates and provide additional conformational information. This model explicitly elucidates the link between the global conformation of a conjugate and the microstructure of its constituent components.

  7. Changes in the Solution Behavior of Conjugated Polymers with Light Absorption

    NASA Astrophysics Data System (ADS)

    Dadmun, Mark; Morgan, Brian

    2015-03-01

    Conjugated polymers are well established as functional materials in a broad range of applications including organic photovoltaics, chemical sensors, and organic light emitting diodes. This functionality is mainly derived from their ability to create electron-hole pair excitons through photoexcitation. The presence of these entities on the polymer chains may alter the chain conformation, solution behavior, and ultimately macroscopic morphology, of the conjugated polymer. Previous studies have shown significant changes in properties such as viscosity and photoluminescence upon exposure of select conjugated polymer films to white light. In order to expand upon these preliminary findings, we have performed small angle neutron scattering experiments on solutions of several semiconducting, conjugated polymers in both the presence and absence of incident light. Substantial differences are observed between the light vs dark samples, the magnitude of which are dependent on polymer dispersion, solvent choice, and solution concentration. Analysis of the neutron curves shows real difference in Kuhn lengths and radius of gyration of the polymer, suggesting possible rearrangement of polymer chain conformation or alteration of polymer chain-solvent interactions.

  8. Slow rupture of polymer films

    NASA Astrophysics Data System (ADS)

    Kliakhandler, Igor

    2004-11-01

    Bursting of soap film is a fast and fascinating process. It turns out that certain polymer films rupture in a somewhat similar fashion, but much slower. The slowness of the process allows one to study the rupture of polymer films with details. The rupture process in Hele-Shaw-like fashion shows remarkable properties, and is a very simple system. It turns out that propagation speed of the rupture is a function of the film thickness, and rheologic properties of the polymer. Experimental results will be compared with theory, together with demonstration of the experiment.

  9. Soft molding lithography of conjugated polymers

    NASA Astrophysics Data System (ADS)

    Pisignano, Dario; Persano, Luana; Cingolani, Roberto; Gigli, Giuseppe; Babudri, Francesco; Farinola, Gianluca M.; Naso, Francesco

    2004-02-01

    We report on the nanopatterning of conjugated polymers by soft molding, and exploit the glass transition of the organic compound in conformal contact with an elastomeric element. We succeeded in printing different compounds with resolution down to 300 nm at temperatures up to 300 °C in vacuum. No significant variation of the photoluminescence (PL) spectra nor heavy degradation of the PL quantum yield was observed after the lithography process. Based on the high resolution achieved and on the well-retained luminescence properties of the patterned compounds, we conclude that high-temperature soft lithography is a valid, flexible and straightforward technique for one-step realization of organic-based devices.

  10. Interfacial Widths of Conjugated Polymer Bilayers

    SciTech Connect

    NCSU; UC Berkeley; UCSB; Advanced Light Source; Garcia, Andres; Yan, Hongping; Sohn, Karen E.; Hexemer, Alexander; Nguyen, Thuc-Quyen; Bazan, Guillermo C.; Kramer, Edward J.; Ade, Harald

    2009-08-13

    The interfaces of conjugated polyelectrolyte (CPE)/poly[2-methoxy-5-(2{prime}-ethylhexyloxy)-p-phenylene vinylene] (MEH-PPV) bilayers cast from differential solvents are shown by resonant soft X-ray reflectivity (RSoXR) to be very smooth and sharp. The chemical interdiffusion due to casting is limited to less than 0.6 nm, and the interface created is thus nearly 'molecularly' sharp. These results demonstrate for the first time and with high precision that the nonpolar MEH-PPV layer is not much disturbed by casting the CPE layer from a polar solvent. A baseline is established for understanding the role of interfacial structure in determining the performance of CPE-based polymer light-emitting diodes. More broadly, we anticipate further applications of RSoXR as an important tool in achieving a deeper understanding of other multilayer organic optoelectronic devices, including multilayer photovoltaic devices.

  11. Polymer decorated gold nanoparticles in nanomedicine conjugates.

    PubMed

    Capek, Ignác

    2017-02-15

    Noble metal, especially gold nanoparticles and their conjugates with biopolymers have immense potential for disease diagnosis and therapy on account of their surface plasmon resonance (SPR) enhanced light scattering and absorption. Conjugation of noble metal nanoparticles to ligands specifically targeted to biomarkers on diseased cells allows molecular-specific imaging and detection of disease. The development of smart gold nanoparticles (AuNPs) that can deliver therapeutics at a sustained rate directly to cancer cells may provide better efficacy and lower toxicity for treating cancer tumors. We highlight some of the promising classes of targeting systems that are under development for the delivery of gold nanoparticles. Nanoparticles designed for biomedical applications are often coated with polymers containing reactive functional groups to conjugate targeting ligands, cell receptors or drugs. Using targeted nanoparticles to deliver chemotherapeutic agents in cancer therapy offers many advantages to improve drug/gene delivery and to overcome many problems associated with conventional radiotherapy and chemotherapy. The targeted nanoparticles were found to be effective in killing cancer cells which were studied using various anticancer assays. Cell morphological analysis shows the changes occurred in cancer cells during the treatment with AuNPs. The results determine the influence of particle size and concentration of AuNPs on their absorption, accumulation, and cytotoxicity in model normal and cancer cells. As the mean particle diameter of the AuNPs decreased, their rate of absorption by the intestinal epithelium cells increased. These results provide important insights into the relationship between the dimensions of AuNPs and their gastrointestinal uptake and potential cytotoxicity. Furthermore gold nanoparticles efficiently convert the absorbed light into localized heat, which can be exploited for the selective laser photothermal therapy of cancer. We also review

  12. Polymer-Drug Conjugates: Recent Development in Clinical Oncology

    PubMed Central

    Li, Chun; Wallace, Sidney

    2008-01-01

    Targeted drug delivery aims to increase the therapeutic index by making more drug molecules available at the diseased sites while reducing systemic drug exposure. In this update, we provide an overview of polymer-drug conjugates that have advanced into the clinical trials. These systems use synthetic water-soluble polymers as the drug carriers. The preclinical pharmacology and recent data in clinical trials with poly(L-glutamic acid)-paclitaxel (PG-TXL) are discussed first. This is followed by a summary of conjugates of a variety of polymeric conjugates with chemotherapeutic agents. Results from early clinical trials of these polymer-drug conjugates have demonstrated several advantages over the corresponding parent drugs, including fewer side effects, enhanced therapeutic efficacy, ease of drug administration, and improved patient compliance. Collectively, these data warrant further clinical development of polymer-drug conjugates as a new class of anticancer agents. PMID:18374448

  13. Statistical conjugated polymers comprising optoelectronically distinct units.

    PubMed

    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.

  14. Advances in Polymer and Polymeric Nanostructures for Protein Conjugation

    PubMed Central

    González-Toro, Daniella C.; Thayumanavan, S.

    2013-01-01

    Linear polymers have been considered the best molecular structures for the formation of efficient protein conjugates due to their biological advantages, synthetic convenience and ease of functionalization. In recent years, much attention has been dedicated to develop synthetic strategies that produce the most control over protein conjugation utilizing linear polymers as scaffolds. As a result, different conjugate models, such as semitelechelic, homotelechelic, heterotelechelic and branched or star polymer conjugates, have been obtained that take advantage of these well-controlled synthetic strategies. Development of protein conjugates using nanostructures and the formation of said nanostructures from protein-polymer bioconjugates are other areas in the protein bioconjugation field. Although several polymer-protein technologies have been developed from these discoveries, few review articles have focused on the design and function of these polymers and nanostructures. This review will highlight some recent advances in protein-linear polymer technologies that employ protein covalent conjugation and successful protein-nanostructure bioconjugates (covalent conjugation as well) that have shown great potential for biological applications. PMID:24058205

  15. Scattering from Colloid-Polymer Conjugates with Excluded Volume Effect

    DOE PAGES

    Li, Xin; Sanchez-Diaz, Luis E.; Smith, Gregory Scott; ...

    2015-01-13

    This work presents scattering functions of conjugates consisting of a colloid particle and a self-avoiding polymer chain as a model for protein-polymer conjugates and nanoparticle-polymer conjugates in solution. The model is directly derived from the two-point correlation function with the inclusion of excluded volume effects. The dependence of the calculated scattering function on the geometric shape of the colloid and polymer stiffness is investigated. The model is able to describe the experimental scattering signature of the solutions of suspending hard particle-polymer conjugates and provide additional conformational information. This model explicitly elucidates the link between the global conformation of a conjugatemore » and the microstructure of its constituent components.« less

  16. Helically assembled π-conjugated polymers with circularly polarized luminescence

    PubMed Central

    Watanabe, Kazuyoshi; Akagi, Kazuo

    2014-01-01

    We review the recent progress in the field of helically assembled π-conjugated polymers, focusing on aromatic conjugated polymers with interchain helical π-stacking that exhibit circularly polarized luminescence (CPL). In Part 1, we discuss optically active polymers with white-colored CPL and the amplification of the circular polarization through liquid crystallinity. In Part 2, we focus on the stimuli-responsive CPL that results from changes in the conformation and aggregation state of π-conjugated molecules and polymers. In Part 3, we discuss the self-assembly of achiral cationic π-conjugated polymers into circularly polarized luminescent supramolecular nanostructures with the aid of other chiral molecules. PMID:27877698

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

    PubMed

    Xu, Lirong; Yang, Liu; Lei, Shengbin

    2012-08-07

    conjugated oligomers and polymers. The information obtained could benefit the understanding of the elements affecting the film morphology and helps the optimization of device performance.

  18. Polymer-cysteamine conjugates: new mucoadhesive excipients for drug delivery?

    PubMed

    Kast, Constantia E; Bernkop-Schnürch, Andreas

    2002-03-02

    In the present study, the features of two new thiolated polymers--the so-called thiomers--were investigated. Mediated by a carbodiimide cysteamine was covalently attached to sodium carboxymethylcellulose (Na-CMC) and neutralised polycarbophil (Na-PCP). Depending on the weight-ratio polymer to cysteamine during the coupling reaction, the resulting CMC-cysteamine conjugate and PCP-cysteamine conjugate showed in maximum 43 +/- 15 and 138 +/- 22 micromole thiol groups per g polymer (mean +/- S.D.; n=3), respectively, which were used for further characterisation. Tensile studies carried out with the CMC-cysteamine conjugate on freshly excised porcine intestinal mucosa displayed no significantly (P<0.01) improved mucoadhesion, whereas, the mucoadhesive properties of the PCP-cysteamine conjugate were increased 2.5-fold compared with the unmodified polymer. The swelling behaviour of the CMC-cysteamine conjugate was uninfluenced by the covalent attachment of the sulfhydryl compound. In contrast the swelling behaviour of the PCP-cysteamine conjugate was improved significantly (P<0.01) versus unmodified PCP. Furthermore, in aqueous solutions the disintegration time of tablets based on the CMC- and PCP-cysteamine conjugates was prolonged 1.5 and 3.2-fold, respectively, in comparison to tablets containing the corresponding unmodified polymers. According to these results, especially the PCP-cysteamine conjugate represents a promising new pharmaceutical excipient for various drug delivery systems.

  19. Recent Advances in Conjugated Polymers for Light Emitting Devices

    PubMed Central

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

    2011-01-01

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

  20. Anomalous Charge Transport in Conjugated Polymers Reveals Underlying Mechanisms of Trapping and Percolation

    PubMed Central

    2016-01-01

    While transport in conjugated polymers has many similarities to that in crystalline inorganic materials, several key differences reveal the unique relationship between the morphology of polymer films and the charge mobility. We develop a model that directly incorporates the molecular properties of the polymer film and correctly predicts these unique transport features. At low degree of polymerization, the increase of the mobility with the polymer chain length reveals trapping at chain ends, and saturation of the mobility at high degree of polymerization results from conformational traps within the chains. Similarly, the inverse field dependence of the mobility reveals that transport on single polymer chains is characterized by the ability of the charge to navigate around kinks and loops in the chain. These insights emphasize the connection between the polymer conformations and the transport and thereby offer a route to designing improved device morphologies through molecular design and materials processing. PMID:28058280

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

    PubMed

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

    2014-09-01

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

  2. Terahertz emission from biased conjugated polymers excited by femtosecond laser pulses

    NASA Astrophysics Data System (ADS)

    Unuma, Takeya; Yamada, Naruki; Kishida, Hideo

    2016-12-01

    We perform terahertz emission spectroscopy to investigate the ultrafast motion of electrons and holes in conjugated polymer films excited by femtosecond laser pulses under in-plane bias electric field. The terahertz waveforms are found to exhibit not the features of free carrier acceleration along bias electric field but a characteristic shape reproduced well by the second time derivative of a delta-function-like polarization. Linear-to-quadratic relations between the terahertz emission amplitude and the excitation intensity are observed for three different conjugated polymers, indicating that the polarization is created by either exciton formation or optical rectification involving two-step excitation via localized states.

  3. Thin film-coated polymer webs

    DOEpatents

    Wenz, Robert P.; Weber, Michael F.; Arudi, Ravindra L.

    1992-02-04

    The present invention relates to thin film-coated polymer webs, and more particularly to thin film electronic devices supported upon a polymer web, wherein the polymer web is treated with a purifying amount of electron beam radiation.

  4. Synthesis of capped TiO2 nanocrystals of controlled shape and their use with MEH-PPV conjugated polymer to develop nanocomposite films for photovoltaic applications

    NASA Astrophysics Data System (ADS)

    Mighri, F.; Duong, Vu Thi Thuy; On, Do Trong; Ajji, A.

    2014-05-01

    This study presents the synthesis details of titanium dioxide (TiO2) nanoparticles (NPs) of different shapes (nanospheres, nanorods and nanorhombics) using oleic acid (OA) and oleyl amine (OM) as capping agents. In order to develop nanocomposite thin films for photovoltaic cells, these TiO2 NPs were carefully dispersed in 2-methoxy-5-(2'-ethylhexyloxy)-p-phenylene vinylene (MEH-PPV) matrix. The properties of synthesized TiO2 NPs and MEH-PPV/TiO2 nanocomposites were characterized using transmission electron microscopy (TEM), thermogravimetric analysis (TGA), UV-Visible spectroscopy, and Photoluminescence technique. It was found that the shape of NPs and the amount of OA and OM surfactants capped on their surface have an effect on their energy bandgap and also on the dispersion quality of MEH-PPV/TiO2 nanocomposites. Even though there was no evidence of chemical bonding between MEH-PPV matrix and TiO2 dispersed NPs, MEH-PPV/TiO2 nanocomposites showed very promising results for light absorption properties and charge transfer at the interface of the conjugated MEH-PPV matrix and TiO2 dispersed NPs, which are two main characteristics for photovoltaic materials.

  5. Synthesis of capped TiO{sub 2} nanocrystals of controlled shape and their use with MEH-PPV conjugated polymer to develop nanocomposite films for photovoltaic applications

    SciTech Connect

    Mighri, F. E-mail: Thi-Thuy-Duong.vu.1@ulaval.ca; Duong, Vu Thi Thuy E-mail: Thi-Thuy-Duong.vu.1@ulaval.ca; On, Do Trong; Ajji, A.

    2014-05-15

    This study presents the synthesis details of titanium dioxide (TiO{sub 2}) nanoparticles (NPs) of different shapes (nanospheres, nanorods and nanorhombics) using oleic acid (OA) and oleyl amine (OM) as capping agents. In order to develop nanocomposite thin films for photovoltaic cells, these TiO{sub 2} NPs were carefully dispersed in 2-methoxy-5-(2'-ethylhexyloxy)-p-phenylene vinylene (MEH-PPV) matrix. The properties of synthesized TiO{sub 2} NPs and MEH-PPV/TiO{sub 2} nanocomposites were characterized using transmission electron microscopy (TEM), thermogravimetric analysis (TGA), UV-Visible spectroscopy, and Photoluminescence technique. It was found that the shape of NPs and the amount of OA and OM surfactants capped on their surface have an effect on their energy bandgap and also on the dispersion quality of MEH-PPV/TiO{sub 2} nanocomposites. Even though there was no evidence of chemical bonding between MEH-PPV matrix and TiO2 dispersed NPs, MEH-PPV/TiO{sub 2} nanocomposites showed very promising results for light absorption properties and charge transfer at the interface of the conjugated MEH-PPV matrix and TiO{sub 2} dispersed NPs, which are two main characteristics for photovoltaic materials.

  6. A photo-oxidation mechanism for patterning and hologram formation in conjugated polymer/glass composites

    NASA Astrophysics Data System (ADS)

    Levi, Ofer; Perepelitsa, Galina; Davidov, Dan; Shalom, Shoshy; Benjamin, Iris; Neumann, Ronny; Agranat, Aharon J.; Avny, Yair

    2000-08-01

    Improved diffraction efficiency was observed in holograms stored in disordered conjugated polymer/glass composites. The conjugated polymers used were alkoxy substituted poly(phenylenevinylne) analogs and the glass matrices were zirconia-organosilica xerogels. Investigation of the mechanism of hologram formation revealed evidence of a photochromic process consisting of light induced photo-oxidation (bleaching) of the embedded conjugated polymer resulting in the formation of an absorption grating and a phase grating. Investigation of the hologram formation revealed that the process was oxygen dependent. Oxygen removal increases hologram formation time by more than an order of magnitude and halves the total hologram efficiency. The oxygen dependence was also highly correlated with photobleaching of the samples and beam interaction of the writing beams. The chemical transformations upon photobleaching were shown by infrared and Raman spectroscopy to involve chain scission and oxidation of the polymer at the vinylic position of the conjugated polymer. Film preparation of the composites was optimized showing a tenfold improvement in the holographic properties compared to our previous results. The optimized treatment method allows for a high, >20%, diffraction efficiency, η, to be obtained for the 2.5-μm-thick polymer/glass films. Light sensitivity was compared for several polymer/glass composites and was correlated to the absorption curves and holographic diffraction efficiency showing that the new composites and film preparation techniques are promising for holographic materials sensitive in the blue and ultraviolet spectral regions. A method of information fixing by preventing oxygen entry to the composite film resulted in a fourfold increase of the erasure time. These findings suggest that holograms can be fixed for a long term by nonoxygen permeable coating, applied after hologram formation.

  7. Band-structure engineering in conjugated 2D polymers.

    PubMed

    Gutzler, Rico

    2016-10-26

    Conjugated polymers find widespread application in (opto)electronic devices, sensing, and as catalysts. Their common one-dimensional structure can be extended into the second dimension to create conjugated planar sheets of covalently linked molecules. Extending π-conjugation into the second dimension unlocks a new class of semiconductive polymers which as a consequence of their unique electronic properties can find usability in numerous applications. In this article the theoretical band structures of a set of conjugated 2D polymers are compared and information on the important characteristics band gap and valence/conduction band dispersion is extracted. The great variance in these characteristics within the investigated set suggests 2D polymers as exciting materials in which band-structure engineering can be used to tailor sheet-like organic materials with desired electronic properties.

  8. Electronic and Morphological Studies of Conjugated Polymers Incorporating a Disk-Shaped Polycyclic Aromatic Hydrocarbon Unit.

    PubMed

    He, Bo; Zhang, Benjamin A; Liu, Feng; Navarro, Amparo; Fernández-Liencres, M Paz; Lu, Ryan; Lo, Kelvin; Chen, Teresa L; Russell, Thomas P; Liu, Yi

    2015-09-16

    As more research findings have shown the correlation between ordering in organic semiconductor thin films and device performance, it is becoming more essential to exercise control of the ordering through structural tuning. Many recent studies have focused on the influence of side chain engineering on polymer packing orientation in thin films. However, the impact of the size and conformation of aromatic surfaces on thin film ordering has not been investigated in great detail. Here we introduce a disk-shaped polycyclic aromatic hydrocarbon building block with a large π surface, namely, thienoazacoronenes (TACs), as a donor monomer for conjugated polymers. A series of medium bandgap conjugated polymers have been synthesized by copolymerizing TAC with electron donating monomers of varying size. The incorporation of the TAC unit in such semiconducting polymers allows a systematic investigation, both experimentally and theoretically, of the relationships between polymer conformation, electronic structure, thin film morphology, and charge transport properties. Field effect transistors based on these polymers have shown good hole mobilities and photoresponses, proving that TAC is a promising building block for high performance optoelectronic materials.

  9. Lipid-peptide-polymer conjugates and nanoparticles thereof

    DOEpatents

    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.

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

    PubMed

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

    2013-11-01

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

  11. Molecular structure and exciton dynamics in organic conjugated polymers

    NASA Astrophysics Data System (ADS)

    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

  12. Controlling Molecular Ordering in Solution-State Conjugated Polymers

    DOE PAGES

    Zhu, Jiahua; Han, Youngkyu; Kumar, Rajeev; ...

    2015-07-17

    Rationally encoding molecular interactions that can control the assembly structure and functional expression in solution of conjugated polymers holds great potential for enabling optimal organic optoelectronic and sensory materials. In this work, we show that thermally-controlled and surfactant-guided assembly of water-soluble conjugated polymers in aqueous solution is a simple and effective strategy to generate optoelectronic materials with desired molecular ordering. We have studied a conjugated polymer consisting of a hydrophobic thiophene backbone and hydrophilic, thermo-responsive ethylene oxide side groups, which shows a step-wise, multi-dimensional assembly in water. By incorporating the polymer into phase-segregated domains of an amphiphilic surfactant in solution,more » we demonstrate that both chain conformation and degree of molecular ordering of the conjugated polymer can be tuned in hexagonal, micellar and lamellar phases of the surfactant solution. The controlled molecular ordering in conjugated polymer assembly is demonstrated as a key factor determining the electronic interaction and optical function.« less

  13. Process for crosslinking and extending conjugated diene-containing polymers

    NASA Technical Reports Server (NTRS)

    Bell, Vernon L. (Inventor); Havens, Stephen J. (Inventor)

    1977-01-01

    A process using a Diels-Alder reaction which increases the molecular weight and/or crosslinks polymers by reacting the polymers with bisunsaturated dienophiles is developed. The polymer comprises at least 75% by weight based on the reaction product, has a molecular weight of at least 5000 and a plurality of conjugated 1,3-diene systems incorporated into the molecular structure. A dienophile reaction with the conjugated 1,3-diene of the polymer is at least 1% by weight based on the reaction product. Examples of the polymer include polyesters, polyamides, polyethers, polysulfones and copolymers. The bisunsaturated dienophiles may include bis-maleimides, bis maleic and bis tumaric esters and amides. This method for expanding the molecular weight chains of the polymers, preferable thermoplastics, is advantageous for processing or fabricating thermoplastics. A low molecular weight thermoplastic is converted to a high molecular weight plastic having improved strength and toughness for use in the completed end use article.

  14. Mesoscopic quantum emitters from deterministic aggregates of conjugated polymers

    PubMed Central

    Stangl, Thomas; Wilhelm, Philipp; Remmerssen, Klaas; Höger, Sigurd; Vogelsang, Jan; Lupton, John M.

    2015-01-01

    An appealing definition of the term “molecule” arises from consideration of the nature of fluorescence, with discrete molecular entities emitting a stream of single photons. We address the question of how large a molecular object may become by growing deterministic aggregates from single conjugated polymer chains. Even particles containing dozens of individual chains still behave as single quantum emitters due to efficient excitation energy transfer, whereas the brightness is raised due to the increased absorption cross-section of the suprastructure. Excitation energy can delocalize between individual polymer chromophores in these aggregates by both coherent and incoherent coupling, which are differentiated by their distinct spectroscopic fingerprints. Coherent coupling is identified by a 10-fold increase in excited-state lifetime and a corresponding spectral red shift. Exciton quenching due to incoherent FRET becomes more significant as aggregate size increases, resulting in single-aggregate emission characterized by strong blinking. This mesoscale approach allows us to identify intermolecular interactions which do not exist in isolated chains and are inaccessible in bulk films where they are present but masked by disorder. PMID:26417079

  15. Monitoring Protein Capsid Assembly with a Conjugated Polymer Strain Sensor.

    PubMed

    Cingil, Hande E; Storm, Ingeborg M; Yorulmaz, Yelda; te Brake, Diane W; de Vries, Renko; Cohen Stuart, Martien A; Sprakel, Joris

    2015-08-12

    Semiconducting polymers owe their optoelectronic properties to the delocalized electronic structure along their conjugated backbone. Their spectral features are therefore uniquely sensitive to the conformation of the polymer, where mechanical stretching of the chain leads to distinct vibronic shifts. Here we demonstrate how the optomechanical response of conjugated polyelectrolytes can be used to detect their encapsulation in a protein capsid. Coating of the sensor polymers by recombinant coat proteins induces their stretching due to steric hindrance between the proteins. The resulting mechanical planarizations lead to pronounced shifts in the vibronic spectra, from which the process of capsid formation can be directly quantified. These results show how the coupling between vibronic states and mechanical stresses inherent to conjugated polymers can be used to noninvasively measure strains at the nanoscale.

  16. Stabilization of Proteins by Polymer Conjugation via ATRP

    DTIC Science & Technology

    2008-08-31

    year basic research effort by ICx-Agentase to study new techniques of modifying native enzymes with polymers via atom transfer radical polymerization ...techniques of modifying native enzymes with polymers via atom transfer radical polymerization to increase their solubility and utility in organic... polymerization of vinyl monomers in aqueous medium to synthesize highly active enzyme- polymer conjugates. In this effort, we proposed to test our

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

    SciTech Connect

    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.

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

    NASA Astrophysics Data System (ADS)

    Coakley, Kevin M.

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

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

    PubMed

    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.

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

    SciTech Connect

    Schanze, Kirk S

    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.

  1. Conjugated polymer-assisted dispersion of single-wall carbon nanotubes: the power of polymer wrapping.

    PubMed

    Samanta, Suman Kalyan; Fritsch, Martin; Scherf, Ullrich; Gomulya, Widianta; Bisri, Satria Zulkarnaen; Loi, Maria Antonietta

    2014-08-19

    coordinates [(n,m) indices]. The polymer wrapping strategy enables the generation of SWNT dispersions containing exclusively semiconducting nanotubes. Toward the applications in electronic devices, until now most applied approach is a direct processing of such SWNT dispersions into the active layer of network-type thin film field effect transistors. However, to achieve promising transistor performance (high mobility and on-off ratio) careful removal of the wrapping polymer chains seems crucial, for example, by washing or ultracentrifugation. More defined positioning of the SWNTs can be accomplished in directed self-assembly procedures. One possible strategy uses diblock copolymers containing a conjugated polymer block as dispersing moiety and a second block for directed self-assembly, for example, a DNA block for specific interaction with complementary DNA strands. Another strategy utilizes reactive side chains for controlled anchoring onto patterned surfaces (e.g., by interaction of thiol-terminated alkyl side chains with gold surfaces). A further promising application of purified SWNT dispersions is the field of organic (all-carbon) or hybrid solar cell devices.

  2. Conjugated Polymer Design and Engineering for Organic Electronics

    NASA Astrophysics Data System (ADS)

    Woo, Claire Hoi Kar

    The molecular structure of a conjugated polymer critically impacts its physical and optoelectronic properties, thus determining its ultimate performance in organic electronic devices. In this work, new polymers and derivatives are designed, synthesized, characterized, and tested in photovoltaic devices. Through device engineering and nanoscale characterization, general structure-function relationships are established to aid the design of the next-generation of high performance polymer semiconductors for organic electronic applications. Using a prototypical conjugated polymer, the influence of backbone regioregularity is examined and found to highly impact polymer crystallinity, solid state morphology and device stability. The investigation of alternative aromatic units in the backbone also led to new understandings in polymer processability and the development of promising materials for organic photovoltaics. Besides the backbone structure, the side chain choice of the polymer can significantly affect material properties and device performance as well. In fact, the side chain substitution can influence both the optoelectronic properties and the physical properties of the polymer. A sterically bulky side chain can be used to tune the donor/acceptor separation distance, which in turn determines the charge separation efficiency. The addition of a polar side group increases the dielectric constant of a polymer and improves overall charge separation. Choosing the appropriate solubilizing group can also induce solid state packing of the polymer and considerably enhance device efficiency. Finally, the influence of post-fabrication processing techniques on the crystallinity and charge transport properties of a polymer is highlighted.

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

    PubMed

    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

  4. Percolation, tie-molecules, and microstructural origins of charge transport in semicrystalline conjugated polymers (Presentation Recording)

    NASA Astrophysics Data System (ADS)

    Mollinger, Sonya A.; Krajina, Brad; Noriega-Manez, Rodrigo J.; Salleo, Alberto; Spakowitz, Andrew J.

    2015-10-01

    Semiconducting polymers play an important role in a wide range of optical and electronic material applications. Polymer thin films that result in the highest performance typically have a complex semicrystalline morphology, indicating that considerable device improvement can be achieved through optimization of microstructural properties. However, the connection between molecular ordering and device performance is difficult to predict due to the current need for a mathematical theory of the physics that dictates charge transport in semiconducting polymers. It is experimentally suggested that efficient transport in such films occurs via connected networks of crystallites. We present an analytical and computational description of semicrystalline conjugated polymer materials that captures the impact of polymer conformation on charge transport in heterogeneous thin films. We first develop an analytical theory for the statistical behavior of a polymer emanating from a crystallite and predict the average distance to the first kink in the chain that traps a charge. We use this analysis to define the conditions for percolation and the consequent efficient transport through a semicrystalline material. We then establish a charge transport model using Monte Carlo simulations that predicts the multi-scale charge transport and crystallite connections. We approximate the thin film as a two-dimensional grid of crystallites embedded in amorphous polymer. The chain conformations in the amorphous region are determined by the wormlike chain model, and the crystallites are assigned fixed mobilities. We use this model to identify limits of charge transport at various time scales for varying fraction of crystallinity.

  5. Novel non-conjugated main-chain hole-transporting polymers for organic electronics application.

    PubMed

    Schelter, Jürgen; Mielke, Georg Felix; Köhnen, Anne; Wies, Jenna; Köber, Sebastian; Nuyken, Oskar; Meerholz, Klaus

    2010-09-01

    A new class of hole-transporting polymers for use in organic electronic devices such as organic light-emitting diodes (OLEDs) or photorefractive holographic storage devices has been synthesized. The polymers contain tetraarylbenzidines or tetraarylphenylenediamines as charge-transporting units in the polymer backbone and are connected by non-conjugating fluorene bridges. For use in OLEDs the novel polymers were functionalized with oxetane groups that can be cross-linked via a cationic ring opening polymerization to yield insoluble networks. Such insoluble films are necessary for the fabrication of multilayer devices by wet deposition techniques. The novel materials feature improved film-formation properties as demonstrated in green-emitting double-layer OLEDs.

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

    PubMed

    Osaka, Itaru; Takimiya, Kazuo

    2017-02-27

    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.

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

    PubMed

    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

  8. Fluorescent non-conjugated polymer dots for targeted cell imaging

    NASA Astrophysics Data System (ADS)

    Sun, Bin; Zhao, Bin; Wang, Dandan; Wang, Yibo; Tang, Qi; Zhu, Shoujun; Yang, Bai; Sun, Hongchen

    2016-05-01

    Through the chemical crosslinking of the sub-fluorophore, linear non-conjugated polymers can possess strong photoluminescence (PL), which is a very important fluorescence behavior and the non-conjugated polymer dots (PDs) are efficient bio-fluorophores for bio-based applications. Herein, the new type of non-conjugated polyethyleneimine (PEI) PDs was further modified by targeting molecules (folic acid) for a new generation of bio-fluorophores. The free folic acid can quench the PL of PDs by energy transfer, while the conjugated folic acid@PDs (FA@PDs) can still maintain their PL properties to a certain degree. The FA@PDs also possess lower toxicity compared with free PDs, which is possibly due to blocking of the amino groups. Moreover, we investigated the targeted bioimaging applications of the FA@PDs, which gave a very important direction for application of these types of materials.Through the chemical crosslinking of the sub-fluorophore, linear non-conjugated polymers can possess strong photoluminescence (PL), which is a very important fluorescence behavior and the non-conjugated polymer dots (PDs) are efficient bio-fluorophores for bio-based applications. Herein, the new type of non-conjugated polyethyleneimine (PEI) PDs was further modified by targeting molecules (folic acid) for a new generation of bio-fluorophores. The free folic acid can quench the PL of PDs by energy transfer, while the conjugated folic acid@PDs (FA@PDs) can still maintain their PL properties to a certain degree. The FA@PDs also possess lower toxicity compared with free PDs, which is possibly due to blocking of the amino groups. Moreover, we investigated the targeted bioimaging applications of the FA@PDs, which gave a very important direction for application of these types of materials. Electronic supplementary information (ESI) available. See DOI: 10.1039/c6nr01909a

  9. Approaching disorder-free transport in high-mobility conjugated polymers.

    PubMed

    Venkateshvaran, Deepak; Nikolka, Mark; Sadhanala, Aditya; Lemaur, Vincent; Zelazny, Mateusz; Kepa, Michal; Hurhangee, Michael; Kronemeijer, Auke Jisk; Pecunia, Vincenzo; Nasrallah, Iyad; Romanov, Igor; Broch, Katharina; McCulloch, Iain; Emin, David; Olivier, Yoann; Cornil, Jerome; Beljonne, David; Sirringhaus, Henning

    2014-11-20

    Conjugated polymers enable the production of flexible semiconductor devices that can be processed from solution at low temperatures. Over the past 25 years, device performance has improved greatly as a wide variety of molecular structures have been studied. However, one major limitation has not been overcome; transport properties in polymer films are still limited by pervasive conformational and energetic disorder. This not only limits the rational design of materials with higher performance, but also prevents the study of physical phenomena associated with an extended π-electron delocalization along the polymer backbone. Here we report a comparative transport study of several high-mobility conjugated polymers by field-effect-modulated Seebeck, transistor and sub-bandgap optical absorption measurements. We show that in several of these polymers, most notably in a recently reported, indacenodithiophene-based donor-acceptor copolymer with a near-amorphous microstructure, the charge transport properties approach intrinsic disorder-free limits at which all molecular sites are thermally accessible. Molecular dynamics simulations identify the origin of this long sought-after regime as a planar, torsion-free backbone conformation that is surprisingly resilient to side-chain disorder. Our results provide molecular-design guidelines for 'disorder-free' conjugated polymers.

  10. Ultrathin Polymer Films for Microlithography

    DTIC Science & Technology

    1988-07-13

    exposure the PINAA was developed in a solution made of 3:7 cellosolve : methanol for 13 seconds. Cellosolve was chosen because it is strong enough to...can achieve on thicker resist (> 100 nm) for the same exposure conditions. Recently, we have exposed 14.3 nrm L-B PMMA films on a high resolution...Polymer Films LB PMMA Spin-Cast PNMA Spin-Cast Novolac (10 wafers) (5 wafers) (5 wafers) Film Thickness 14.3 nrm 14 nrm 22 nm Pinhole Density < 10/cm 2

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

    PubMed

    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.

  12. Polymer film composite transducer

    DOEpatents

    Owen, Thomas E.

    2005-09-20

    A composite piezoelectric transducer, whose piezoeletric element is a "ribbon wound" film of piezolectric material. As the film is excited, it expands and contracts, which results in expansion and contraction of the diameter of the entire ribbon winding. This is accompanied by expansion and contraction of the thickness of the ribbon winding, such that the sound radiating plate may be placed on the side of the winding.

  13. Hybrid zinc oxide conjugated polymer bulk heterojunction solar cells.

    PubMed

    Beek, Waldo J E; Wienk, Martijn M; Kemerink, Martijn; Yang, Xiaoniu; Janssen, René A J

    2005-05-19

    Bulk heterojunction photovoltaic devices based on blends of a conjugated polymer poly[2-methoxy-5-(3',7'-dimethyloctyloxy)-1,4-phenylenevinylene] (MDMO-PPV) as electron donor and crystalline ZnO nanoparticles (nc-ZnO) as electron acceptor have been studied. Composite nc-ZnO:MDMO-PPV films were cast from a common solvent mixture. Time-resolved pump-probe spectroscopy revealed that a photoinduced electron transfer from MDMO-PPV to nc-ZnO occurs in these blends on a sub-picosecond time scale and produces a long-lived (milliseconds) charge-separated state. The photovoltaic effect in devices, made by sandwiching the active nc-ZnO:MDMO-PPV layer between charge-selective electrodes, has been studied as a function of the ZnO concentration and the thickness of the layer. We also investigated changing the degree and type of mixing of the two components through the use of a surfactant for ZnO and by altering the size and shape of the nc-ZnO particles. Optimized devices have an estimated AM1.5 performance of 1.6% with incident photon to current conversion efficiencies up to 50%. Photoluminescence spectroscopy, atomic force microscopy, and transmission electron microscopy have been used to gain insight in the morphology of these blends.

  14. Cyclodextrin insulation prevents static quenching of conjugated polymer fluorescence at the single molecule level.

    PubMed

    Thomsson, Daniel; Camacho, Rafael; Tian, Yuxi; Yadav, Dheerendra; Sforazzini, Giuseppe; Anderson, Harry L; Scheblykin, Ivan G

    2013-08-12

    Conjugated polymers (CPs) are promising materials for fluorescence imaging application. However, a significant problem in this field is the unexplained abnormally low fluorescence brightness (or number of fluorescence photons detected per one excitation photon) exhibited by most of CP single chains in solid polymer hosts. Here it is shown that this detrimental effect can be fully avoided for short chains of polyfluorene-bis-vinylphenylene (PFBV) embedded in a host polymer matrix of PMMA, if the conjugated backbone is insulated by cyclodextrin rings to form a polyrotaxane (PFBV-Rtx). Fluorescence kinetics and quantum yields are measured for the polymers in liquid solutions, pristine films, and solid PMMA blends. The fluorescence brightness of PFBV-Rtx single chains dispersed in a solid PMMA is very close to that expected for a chain with 100% fluorescence quantum yield, while the unprotected PFBV chains of the same length possess 4 times lower brightness. Despite this, the fluorescence decay kinetics are the same for both polymers, suggesting the presence of static or ultrafast fluorescence quenching in the unprotected polymer. About 80% of an unprotected PFBV chain is estimated to be completely quenched. The hypothesis is that the cyclodextrin rings prevent the quenching by working as 'bumpers' reducing the mechanical forces applied by the host polymer to the conjugated backbone and help retaining its conformational freedom. While providing a recipe for making CP fluorescence bright at the single-molecule level, these results identify a lack of fundamental understanding in the community of the influence of the environment on excited states in conjugated materials.

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

    PubMed

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

    2016-08-03

    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 substrate with solution-state disentanglement and preaggregation of P3HT in a θ solvent, leading to a very significant enhancement of the field effect carrier mobility. The preaggregation 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 preaggregation alone. In situ quartz crystal microbalance with dissipation (QCM-D) experiments reveal enhanced deposition of preaggregates on surfaces modified with an alkyl-terminated self-assembled monolayer (SAM) in comparison to unaggregated polymer chains in the same conditions. Additional measurements reveal the combined preaggregation 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 preaggregation with substrate chemical functionalization, to enhance the polymer self-assembly and improve its interfacial order with benefits for transport properties.

  16. Recent Advances in Conjugated Polymer Materials for Disease Diagnosis.

    PubMed

    Lv, Fengting; Qiu, Tian; Liu, Libing; Ying, Jianming; Wang, Shu

    2016-02-10

    The extraordinary optical amplification and light-harvesting properties of conjugated polymers impart sensing systems with higher sensitivity, which meets the primary demands of early cancer diagnosis. Recent advances in the detection of DNA methylation and mutation with polyfluorene derivatives based fluorescence resonance energy transfer (FRET) as a means to modulate fluorescent responses attest to the great promise of conjugated polymers as powerful tools for the clinical diagnosis of diseases. To facilitate the ever-changing needs of diagnosis, the development of detection approaches and FRET signal analysis are highlighted in this review. Due to their exceptional brightness, excellent photostability, and low or absent toxicity, conjugated polymers are verified as superior materials for in-vivo imaging, and provide feasibility for future clinical molecular-imaging applications. The integration of conjugated polymers with clinical research has shown profound effects on diagnosis for the early detection of disease-related biomarkers, as well as in-vivo imaging, which leads to a multidisciplinary scientific field with perspectives in both basic research and application issues.

  17. Patterning of conjugated polymers for organic optoelectronic devices.

    PubMed

    Xu, Youyong; Zhang, Fan; Feng, Xinliang

    2011-05-23

    Conjugated polymers have been attracting more and more attention because they possess various novel electrical, magnetical, and optical properties, which render them useful in modern organic optoelectronic devices. Due to their organic nature, conjugated polymers are light-weight and can be fabricated into flexible appliances. Significant research efforts have been devoted to developing new organic materials to make them competitive with their conventional inorganic counterparts. It is foreseeable that when large-scale industrial manufacture of the devices made from organic conjugated polymers is feasible, they would be much cheaper and have more functions. On one hand, in order to improve the performance of organic optoelectronic devices, it is essential to tune their surface morphologies by techniques such as patterning. On the other hand, patterning is the routine requirement for device processing. In this review, the recent progress in the patterning of conjugated polymers for high-performance optoelectronic devices is summarized. Patterning based on the bottom-up and top-down methods are introduced. Emerging new patterning strategies and future trends for conventional patterning techniques are discussed.

  18. Self-assembled breath figure arrays of conjugated conducting polymers for photovoltaic application

    NASA Astrophysics Data System (ADS)

    Routh, Prahlad Kumar; Venkatesh, T. A.; Cotlet, Mircea

    2014-03-01

    Ordered microporous polymer structures have potential application in catalysis, surface engineering and optoelectronics. The Breath Figure Technique (BFT) is a simple method of producing such ordered microporous structures. In this study BFT was applied to a series of commercial conjugated polymer polythiophene derivatives with varying side chain length (n =6,8,10,12). An in-depth study of processing parameters has been carried with the aim of controlling the morphology of the honeycomb film over large, PV relevant areas. Structural and spectroscopic characterization of honeycomb films were performed using Scanning Electron Microscopy (SEM), X-ray scattering, Fluorescence Lifetime Imaging (FLIM) and Spectroscopy. Blends of these polymers with a fullerene derivative, PCBM, were also subjected to BFT and characterized with similar methods to assess their potential use as active layers in PV solar cells. Center for Functional Nanomaterials, Brookhaven National Laboratory.

  19. Magnetic conjugated polymer nanoparticles as bimodal imaging agents.

    PubMed

    Howes, Philip; Green, Mark; Bowers, Alex; Parker, David; Varma, Gopal; Kallumadil, Mathew; Hughes, Mary; Warley, Alice; Brain, Anthony; Botnar, Rene

    2010-07-21

    Hybrid nanoparticles which incorporate multiple functionalities, such as fluorescence and magnetism, can exhibit enhanced efficiency and versatility by performing several tasks in parallel. In this study, magnetic-fluorescent semiconductor polymer nanospheres (MF-SPNs) have been synthesized by encapsulation of hydrophobic conjugated polymers and iron oxide nanoparticles in phospholipid micelles. Four fluorescent conjugated polymers were used, yielding aqueous dispersions of nanoparticles which emit across the visible spectrum. The MF-SPNs were shown to be magnetically responsive and simultaneously fluorescent. In MRI studies, they were seen to have a shortening effect on the transverse T(2)* relaxation time, which demonstrates their potential as an MR contrast agent. Finally, successful uptake of the MF-SPNs by SH-SY5Y neuroblastoma cells was demonstrated, and they were seen to behave as bright and stable fluorescent markers. There was no evidence of toxicity or adverse affect on cell growth.

  20. Dirac Cones in two-dimensional conjugated polymer networks

    NASA Astrophysics Data System (ADS)

    Adjizian, Jean-Joseph; Briddon, Patrick; Humbert, Bernard; Duvail, Jean-Luc; Wagner, Philipp; Adda, Coline; Ewels, Christopher

    2014-12-01

    Linear electronic band dispersion and the associated Dirac physics has to date been limited to special-case materials, notably graphene and the surfaces of three-dimensional (3D) topological insulators. Here we report that it is possible to create two-dimensional fully conjugated polymer networks with corresponding conical valence and conduction bands and linear energy dispersion at the Fermi level. This is possible for a wide range of polymer types and connectors, resulting in a versatile new family of experimentally realisable materials with unique tuneable electronic properties. We demonstrate their stability on substrates and possibilities for doping and Dirac cone distortion. Notably, the cones can be maintained in 3D-layered crystals. Resembling covalent organic frameworks, these materials represent a potentially exciting new field combining the unique Dirac physics of graphene with the structural flexibility and design opportunities of organic-conjugated polymer chemistry.

  1. Synthesis of biotinylated aldehyde polymers for biomolecule conjugation.

    PubMed

    Alconcel, Steevens N S; Kim, Sung Hye; Tao, Lei; Maynard, Heather D

    2013-06-25

    Biotinylated polymers with side-chain aldehydes were prepared for use as multifunctional scaffolds. Two different biotin-containing chain transfer agents (CTAs) and an aldehyde-containing monomer, 6-oxohexyl acrylate (6OHA), are synthesized. Poly(ethylene glycol) methyl ether acrylate (PEGA) and 6OHA are copolymerized by reversible addition-fragmentation chain transfer (RAFT) polymerization in the presence of the biotinylated CTAs. The resulting polymers are analyzed by GPC and(1) H NMR spectroscopy. The polymer end groups contained a disulfide bond, which could be readily reduced in solution to remove the biotin. Reactivity of the aldehyde side chains is demonstrated by oxime and hydrazone formation at the polymer side chains, and conjugate formation of fluorescently labeled polymers with streptavidin is investigated by gel electrophoresis.

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

    PubMed

    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.

  3. Light-evoked hyperpolarization and silencing of neurons by conjugated polymers

    NASA Astrophysics Data System (ADS)

    Feyen, Paul; Colombo, Elisabetta; Endeman, Duco; Nova, Mattia; Laudato, Lucia; Martino, Nicola; Antognazza, Maria Rosa; Lanzani, Guglielmo; Benfenati, Fabio; Ghezzi, Diego

    2016-03-01

    The ability to control and modulate the action potential firing in neurons represents a powerful tool for neuroscience research and clinical applications. While neuronal excitation has been achieved with many tools, including electrical and optical stimulation, hyperpolarization and neuronal inhibition are typically obtained through patch-clamp or optogenetic manipulations. Here we report the use of conjugated polymer films interfaced with neurons for inducing a light-mediated inhibition of their electrical activity. We show that prolonged illumination of the interface triggers a sustained hyperpolarization of the neuronal membrane that significantly reduces both spontaneous and evoked action potential firing. We demonstrate that the polymeric interface can be activated by either visible or infrared light and is capable of modulating neuronal activity in brain slices and explanted retinas. These findings prove the ability of conjugated polymers to tune neuronal firing and suggest their potential application for the in-vivo modulation of neuronal activity.

  4. Light-evoked hyperpolarization and silencing of neurons by conjugated polymers

    PubMed Central

    Feyen, Paul; Colombo, Elisabetta; Endeman, Duco; Nova, Mattia; Laudato, Lucia; Martino, Nicola; Antognazza, Maria Rosa; Lanzani, Guglielmo; Benfenati, Fabio; Ghezzi, Diego

    2016-01-01

    The ability to control and modulate the action potential firing in neurons represents a powerful tool for neuroscience research and clinical applications. While neuronal excitation has been achieved with many tools, including electrical and optical stimulation, hyperpolarization and neuronal inhibition are typically obtained through patch-clamp or optogenetic manipulations. Here we report the use of conjugated polymer films interfaced with neurons for inducing a light-mediated inhibition of their electrical activity. We show that prolonged illumination of the interface triggers a sustained hyperpolarization of the neuronal membrane that significantly reduces both spontaneous and evoked action potential firing. We demonstrate that the polymeric interface can be activated by either visible or infrared light and is capable of modulating neuronal activity in brain slices and explanted retinas. These findings prove the ability of conjugated polymers to tune neuronal firing and suggest their potential application for the in-vivo modulation of neuronal activity. PMID:26940513

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

    PubMed

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

    2014-11-10

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

  6. Preparation of patterned ultrathin polymer films.

    PubMed

    Yang, Huige; Su, Meng; Li, Kaiyong; Jiang, Lei; Song, Yanlin; Doi, Masao; Wang, Jianjun

    2014-08-12

    Though patterned ultrathin polymer films (<100 nm) are of great importance in the fields of sensors and nanoelectronic devices, the fabrication of patterned ultrathin polymer films remains a great challenge. Herein, patterned ultrathin polymer films are fabricated facilely on hydrophobic substrates with different hydrophilic outline patterns by the pinning of three-phase contact lines of polymer solution on the hydrophilic outlines. This method is universal for most of the water-soluble polymers, and poly(vinyl alcohol) (PVA) has been selected as a model polymer due to its biocompatibility and good film-forming property. The results indicate that the morphologies of ultrathin polymer films can be precisely adjusted by the size of the hydrophilic outline pattern. Specifically, patterned hydrophilic outlines with sizes of 100, 60, and 40 μm lead to the formation of concave-shaped ultrathin PVA films, whereas uniform ultrathin PVA films are formed on 20 and 10 μm patterned substrates. The controllabilities of morphologies can be interpreted through the influences of the slip length and coffee ring effect. Theoretical analysis shows that when the size of the hydrophilic outline patterns is smaller than a critical value, the coffee ring effect disappears and uniform patterned ultrathin polymer films can be formed for all polymer concentrations. These results provide an effective methodology for the fabrication of patterned ultrathin polymer films and enhance the understanding of the coffee ring effect.

  7. Glass transition dynamics and charge carrier mobility in conjugated polyfluorene thin films

    NASA Astrophysics Data System (ADS)

    Qin, Hui; Liu, Dan; Wang, Tao

    Conjugated polymers are commonly used in organic optoelectronic devices, e.g. organic photovoltaics (OPVs), light-emitting diodes (LEDs) and field effect transistors (FETs). In these devices, the conjugated polymers are prepared as thin films with thicknesses in the range of tens to hundreds of nanometers, and are interfaced with different function layers made from organic or inorganic materials. We have studied the glass transition temperature (Tg) of poly(9, 9-dioctylfluorene)-co-N-(1, 4-butylphenyl)diphenylamine) (TFB) thin films supported on different substrates, as well as their SCLC charge carrier mobility in photodiodes. Both Monotonic and non-monotonic Tg deviations are observed in TFB thin films supported on Si/SiOx and PEDOT:PSS, respectively. With low to moderate thermal crosslinking, the thickness dependent Tg deviation still exists, which diminishes in TFB films with a high crosslinking degree. The vertical charge carrier mobility of TFB thin films extracted from the SCLC measurements is found increase with film thickness, a value increases from 1 to 50 x 10-6 cm2 V-1 s-1 in the thickness range from 15 to 180 nm. Crosslinking was found to reduce the carrier mobility in TFB thin films. The Tg deviations are also discussed using the classic layered models in the literature. Our results provide a precise guide for the fabrication and design of high performance optoelectronic devices.

  8. Characterization of naproxen-polymer conjugates for drug-delivery.

    PubMed

    Forte, Gianpiero; Chiarotto, Isabella; Giannicchi, Ilaria; Loreto, Maria Antonietta; Martinelli, Andrea; Micci, Roberta; Pepi, Federico; Rossi, Serena; Salvitti, Chiara; Stringaro, Annarita; Tortora, Luca; Vecchio Ciprioti, Stefano; Feroci, Marta

    2016-01-01

    The synthesis and the characterization of three new naproxen decorated polymers are described. A versatile and general approach is employed to link the drug to polymers, affording the derivatives with a very high degree of purity. The release of the drug from the conjugates proved to be exceptionally slow, even in acidic aqueous media, and the kinetic of the process seems to be triggered by their solubility in water. On the other hand, the interesting outcome of the first ex vivo drug release experiments on human blood samples makes this preliminary study valuable for future investigations on the use of these polymeric prodrugs in in vivo treatment of inflammatory states.

  9. Conjugated polymer composite nanoparticles by rapid mixing.

    PubMed

    Jung, Christoph; de Roo, Tjaard; Mecking, Stefan

    2014-12-01

    Composite nanoparticles from poly[(9,9-di-n-octylfluoren-2,7-diyl)-alt-(benzo[2,1,3]thiadiazol-4,8-diyl)] (F8BT) and poly(9,9-di-n-hexylfluoren-2,7-diyl) (PF) with embedded inorganic nanoparticles (TiO2 , CdSe, and CdSe/CdS) are prepared through kinetic trapping by rapid turbulent mixing in a multi-inlet vortex mixer without the need for polymer functionalization. High contents of inorganic materials up to 50-60 wt% are realized for all composites. The influence of flow ratios, sodium dodecyl sulfate (SDS) concentration, and absolute flow rates on the particle size and morphology is studied. High water-to-THF ratios and high total flow rates around 2 m s(-1) yield particle sizes below 50 nm. By adjusting these parameters, controlled particle sizes between 30 to several hundred nanometers are obtained. Composite particles from CdSe/CdS and F8BT or PF show a strong quenching of the polymer emission and near exclusive emission from the inorganic nanocrystal, which indicates an efficient energy transfer with fluorescence quantum yields of 23% for the F8BT/CdSe/CdS composites and 21% for the PF/CdSe/CdS composites. The dispersions are colloidally stable for several months.

  10. Ultrafast polarisation spectroscopy of photoinduced charges in a conjugated polymer

    SciTech Connect

    Bakulin, A A; Loosdrecht, P van; Pshenichnikov, M S; Parashchuk, D Yu

    2009-07-31

    Tunable optical parametric generators and amplifiers (OPA), proposed and developed by Akhmanov and his colleagues, have become the working horses in exploration of dynamical processes in physics, chemistry, and biology. In this paper, we demonstrate the possibility of using ultrafast polarisation-sensitive two-colour spectroscopy, performed with a set of two OPAs, to study charge photogeneration and transport in conjugated polymers and their donor-acceptor blends. (special issue devoted to the 80th birthday of S.A. Akhmanov)

  11. Accurate Force Field Development for Modeling Conjugated Polymers.

    PubMed

    DuBay, Kateri H; Hall, Michelle Lynn; Hughes, Thomas F; Wu, Chuanjie; Reichman, David R; Friesner, Richard A

    2012-11-13

    The modeling of the conformational properties of conjugated polymers entails a unique challenge for classical force fields. Conjugation imposes strong constraints upon bond rotation. Planar configurations are favored, but the concomitantly shortened bond lengths result in moieties being brought into closer proximity than usual. The ensuing steric repulsions are particularly severe in the presence of side chains, straining angles, and stretching bonds to a degree infrequently found in nonconjugated systems. We herein demonstrate the resulting inaccuracies by comparing the LMP2-calculated inter-ring torsion potentials for a series of substituted stilbenes and bithiophenes to those calculated using standard classical force fields. We then implement adjustments to the OPLS-2005 force field in order to improve its ability to model such systems. Finally, we show the impact of these changes on the dihedral angle distributions, persistence lengths, and conjugation length distributions observed during molecular dynamics simulations of poly[2-methoxy-5-(2'-ethylhexyloxy)-p-phenylene vinylene] (MEH-PPV) and poly 3-hexylthiophene (P3HT), two of the most widely used conjugated polymers.

  12. Molecules with enhanced electronic polarizabilities based on defect-like states in conjugated polymers

    NASA Technical Reports Server (NTRS)

    Beratan, David N. (Inventor)

    1991-01-01

    Highly conjugated organic polymers typically have large non-resonant electronic susceptibilities, which give the molecules unusual optical properties. To enhance these properties, defects are introduced into the polymer chain. Examples include light doping of the conjugated polymer and synthesis, conjugated polymers which incorporate either electron donating or accepting groups, and conjugated polymers which contain a photoexcitable species capable of reversibly transferring its electron to an acceptor. Such defects in the chain permit enhancement of the second hyperpolarizability by at least an order of magnitude.

  13. Liquid film/polymer interfaces

    SciTech Connect

    Allara, David L.

    2003-06-12

    The objectives were: (1) Through experimental studies, advance the fundamental understanding of the principles that govern adsorption and wetting phenomena at polymer and organic surfaces. (2) Establish a firm scientific basis for improving the design of coatings for metal fin cooling surfaces used to control the wetting of water condensate for optimum energy efficiency. Several important findings were: (1) water adsorbed at hydrophobic surfaces has a liquid-like structure, in contrast to the generally held view of an ordered structure; (2) Correlations of large amounts of contact angle wetting data of grafted alkyl chain compounds showed a distinct link between the contact angle and the conformational ordering of the chains; (3) water adsorption at long chain alkysiloxane films showed a strong pH dependence on the film stability, which can be attributed to interfacial chemical effects on the siloxane network.

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

    SciTech Connect

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

    2012-07-30

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

  15. High temperature polymer dielectric film insulation

    NASA Technical Reports Server (NTRS)

    Jones, Robert J.

    1994-01-01

    PFPI polymers were invented in the late 1970's. Assessment of emerging requirements has dictated that 300 C performance is the goal for next generation wire insulation. TRW PFPI as superior 300 C polymer candidates is presented. Included is a comparison of promising PFPI film properties with Kapton. Also included are the promising bulk polymer or coating properties.

  16. Spray forming polymer membranes, coatings and films

    DOEpatents

    McHugh, Kevin M.; Watson, Lloyd D.; McAtee, Richard E.; Ploger, Scott A.

    1993-01-01

    A method of forming a polymer film having controlled physical and chemical characteristics, wherein a plume of nebulized droplets of a polymer or polymer precursor is directed toward a substrate from a converging/diverging nozzle having a throat at which the polymer or a precursor thereof is introduced and an exit from which the nebulized droplets of the polymer or precursor thereof leave entrained in a carrier gas. Relative movement between the nozzle and the substrate is provided to form a polymer film. Physical and chemical characteristics can be controlled by varying the deposition parameters and the gas and liquid chemistries. Semipermeable membranes of polyphosphazene films are disclosed, as are a variety of other polymer systems, both porous and non-porous.

  17. Spray forming polymer membranes, coatings and films

    DOEpatents

    McHugh, K.M.; Watson, L.D.; McAtee, R.E.; Ploger, S.A.

    1993-10-12

    A method is described for forming a polymer film having controlled physical and chemical characteristics, wherein a plume of nebulized droplets of a polymer or polymer precursor is directed toward a substrate from a converging/diverging nozzle having a throat at which the polymer or a precursor thereof is introduced and an exit from which the nebulized droplets of the polymer or precursor thereof leave entrained in a carrier gas. Relative movement between the nozzle and the substrate is provided to form a polymer film. Physical and chemical characteristics can be controlled by varying the deposition parameters and the gas and liquid chemistries. Semipermeable membranes of polyphosphazene films are disclosed, as are a variety of other polymer systems, both porous and non-porous. 4 figures.

  18. Light-emitting conjugated polymers with microporous network architecture: interweaving scaffold promotes electronic conjugation, facilitates exciton migration, and improves luminescence.

    PubMed

    Xu, Yanhong; Chen, Long; Guo, Zhaoqi; Nagai, Atsushi; Jiang, Donglin

    2011-11-09

    Herein we report a strategy for the design of highly luminescent conjugated polymers by restricting rotation of the polymer building blocks through a microporous network architecture. We demonstrate this concept using tetraphenylethene (TPE) as a building block to construct a light-emitting conjugated microporous polymer. The interlocked network successfully restricted the rotation of the phenyl units, which are the major cause of fluorescence deactivation in TPE, thus providing intrinsic luminescence activity for the polymers. We show positive "CMP effects" that the network promotes π-conjugation, facilitates exciton migration, and improves luminescence activity. Although the monomer and linear polymer analogue in solvents are nonemissive, the network polymers are highly luminescent in various solvents and the solid state. Because emission losses due to rotation are ubiquitous among small chromophores, this strategy can be generalized for the de novo design of light-emitting materials by integrating the chromophores into an interlocked network architecture.

  19. Conjugation of bioactive groups to poly(lactic acid) and poly[(lactic acid)-co-(glycolic acid)] films.

    PubMed

    Prime, Emma L; Cooper-White, Justin J; Qiao, Greg G

    2007-12-06

    A novel PLA-based polymer containing reactive pendent ketone or hydroxyl groups was synthesized by the copolymerization of L-lactide with epsilon-caprolactone-based monomers. The polymer was activated with NPC, resulting in an amine-reactive polymer which was then cast into thin polymeric films, either alone or as part of a blend with PLGA, before immersion into a solution of the cell adhesion peptide GRGDS in PBS buffer allowed for conjugation of GRGDS to the film surfaces. Subsequent 3T3 fibroblast cell adhesion studies demonstrated an increase in cellular adhesion and spreading over films cast from unmodified PLGA. Hence the new polymer can be used to obtain covalent linkage of amine-containing molecules to polymer surfaces.

  20. Novel Effects of Compressed CO2 Molecules on Structural Ordering and Charge Transport in Conjugated Poly(3-hexylthiophene) Thin Films

    DOE PAGES

    Jiang, Naisheng; Sendogdular, Levent; Sen, Mani; ...

    2016-10-06

    We report the effects of compressed CO2 molecules as a novel plasticization agent for poly(3- hexylthiophene) (P3HT) conjugated polymer thin films. In-situ neutron reflectivity experiment demonstrated the excess sorption of CO2 molecules in the P3HT thin films (about 40 nm in thickness) at low pressure (P = 8.2 MPa) under the isothermal condition of T = 36 °C, which is far below the polymer bulk melting point. The results evidenced that these CO2 molecules accelerated the crystallization process of the polymer on the basis of ex-situ grazing incidence Xray diffraction measurements after drying the films via rapid depressurization to atmosphericmore » pressure: not only the out-of-plane lamellar ordering of the backbone chains but also intra-plane π-π stacking of the side chains were significantly improved, when compared to those in the control P3HT films subjected to conventional thermal annealing (at T = 170 °C). Electrical measurements elucidated that the CO2-annealed P3HT thin films exhibited enhanced charge carrier mobility along with decreased background charge carrier concentration and trap density compared to those in the thermally annealed counterpart. This is attributed to the CO2-induced increase in polymer chain mobility that can drive the detrapping of molecular oxygen and healing of conformational defects in the polymer thin film. Given the universality of the excess sorption of CO2regardless of the type of polymers, the present findings suggest that the CO2 annealing near the critical point can be useful as a robust processing strategy for improving structural and electrical characteristics of other semiconducting conjugated polymers and related systems such as polymer: fullerene bulk heterojunction films.tion films.« less

  1. Role of redox centre in charge transport investigated by novel self-assembled conjugated polymer molecular junctions

    PubMed Central

    Wang, Zongrui; Dong, Huanli; Li, Tao; Hviid, Rune; Zou, Ye; Wei, Zhongming; Fu, Xiaolong; Wang, Erjing; Zhen, Yonggang; Nørgaard, Kasper; Laursen, Bo W.; Hu, Wenping

    2015-01-01

    Molecular electronics describes a field that seeks to implement electronic components made of molecular building blocks. To date, few studies have used conjugated polymers in molecular junctions despite the fact that they potentially transport charge more efficiently than the extensively investigated small-molecular systems. Here we report a novel type of molecular tunnelling junction exploring the use of conjugated polymers, which are self-assembled into ultrathin films in a distinguishable ‘planar' manner from the traditional vertically oriented small-molecule monolayers. Electrical measurements on the junctions reveal molecular-specific characteristics of the polymeric molecules in comparison with less conjugated small molecules. More significantly, we decorate redox-active functionality into polymeric backbones, demonstrating a key role of redox centre in the modulation of charge transport behaviour via energy level engineering and external stimuli, and implying the potential of employing tailor-made polymeric components as alternatives to small molecules for future molecular-scale electronics. PMID:26085081

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

    PubMed

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

    2001-09-11

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

  3. Hydrochromic conjugated polymers for human sweat pore mapping

    NASA Astrophysics Data System (ADS)

    Lee, Joosub; Pyo, Minkyeong; Lee, Sang-Hwa; Kim, Jaeyong; Ra, Moonsoo; Kim, Whoi-Yul; Park, Bum Jun; Lee, Chan Woo; Kim, Jong-Man

    2014-04-01

    Hydrochromic materials have been actively investigated in the context of humidity sensing and measuring water contents in organic solvents. Here we report a sensor system that undergoes a brilliant blue-to-red colour transition as well as ‘Turn-On’ fluorescence upon exposure to water. Introduction of a hygroscopic element into a supramolecularly assembled polydiacetylene results in a hydrochromic conjugated polymer that is rapidly responsive (<20 μs), spin-coatable and inkjet-compatible. Importantly, the hydrochromic sensor is found to be suitable for mapping human sweat pores. The exceedingly small quantities (sub-nanolitre) of water secreted from sweat pores are sufficient to promote an instantaneous colorimetric transition of the polymer. As a result, the sensor can be used to construct a precise map of active sweat pores on fingertips. The sensor technology, developed in this study, has the potential of serving as new method for fingerprint analysis and for the clinical diagnosis of malfunctioning sweat pores.

  4. Hydrochromic conjugated polymers for human sweat pore mapping.

    PubMed

    Lee, Joosub; Pyo, Minkyeong; Lee, Sang-hwa; Kim, Jaeyong; Ra, Moonsoo; Kim, Whoi-Yul; Park, Bum Jun; Lee, Chan Woo; Kim, Jong-Man

    2014-04-29

    Hydrochromic materials have been actively investigated in the context of humidity sensing and measuring water contents in organic solvents. Here we report a sensor system that undergoes a brilliant blue-to-red colour transition as well as 'Turn-On' fluorescence upon exposure to water. Introduction of a hygroscopic element into a supramolecularly assembled polydiacetylene results in a hydrochromic conjugated polymer that is rapidly responsive (<20 μs), spin-coatable and inkjet-compatible. Importantly, the hydrochromic sensor is found to be suitable for mapping human sweat pores. The exceedingly small quantities (sub-nanolitre) of water secreted from sweat pores are sufficient to promote an instantaneous colorimetric transition of the polymer. As a result, the sensor can be used to construct a precise map of active sweat pores on fingertips. The sensor technology, developed in this study, has the potential of serving as new method for fingerprint analysis and for the clinical diagnosis of malfunctioning sweat pores.

  5. Highly Ordered Single Conjugated Polymer Chain Rod Morphologies

    SciTech Connect

    Adachi, Takuji; Brazard, Johanna; Chokshi, Paresh; Ganesan, Venkat; Bolinger, Joshua; Barbara, Paul F.

    2010-10-15

    We have reexamined the fluorescence polarization anisotropy of single polymer chains of the prototypical conjugated polymer poly[2-methoxy-5-(2'-ethylhexyloxy)-1,4-phenylenevinylene] (MEH-PPV) isolated in a poly(methyl methacrylate) (PMMA) matrix employing improved synthetic samples that contain a much smaller number of tetrahedral chemical defects per chain. The new measurements reveal a much larger fraction of highly anisotropic MEH-PPV chains, with >70% of the chains exhibiting polarization anisotropy values falling in the range of 0.6-0.9. High anisotropy is strong evidence for a rod-shaped conformation. A comparison of the experimental results with coarse grain, beads on a chain simulations reveals that simulations with the usual bead-bead pairwise additive potentials cannot reproduce the observed large fraction of high polarization values. Apparently, this type of potential lacks some yet to be identified molecular feature that is necessary to accurately simulate the experimental results.

  6. Sustained gastrointestinal activity of dendronized polymer-enzyme conjugates

    NASA Astrophysics Data System (ADS)

    Fuhrmann, Gregor; Grotzky, Andrea; Lukić, Ružica; Matoori, Simon; Luciani, Paola; Yu, Hao; Zhang, Baozhong; Walde, Peter; Schlüter, A. Dieter; Gauthier, Marc A.; Leroux, Jean-Christophe

    2013-07-01

    Methods to stabilize and retain enzyme activity in the gastrointestinal tract are investigated rarely because of the difficulty of protecting proteins from an environment that has evolved to promote their digestion. Preventing the degradation of enzymes under these conditions, however, is critical for the development of new protein-based oral therapies. Here we show that covalent conjugation to polymers can stabilize orally administered therapeutic enzymes at different locations in the gastrointestinal tract. Architecturally and functionally diverse polymers are used to protect enzymes sterically from inactivation and to promote interactions with mucin on the stomach wall. Using this approach the in vivo activity of enzymes can be sustained for several hours in the stomach and/or in the small intestine. These findings provide new insight and a firm basis for the development of new therapeutic and imaging strategies based on orally administered proteins using a simple and accessible technology.

  7. Diketopyrrolopyrrole-based Conjugated Polymers Bearing Branched Oligo(Ethylene Glycol) Side Chains for Photovoltaic Devices.

    PubMed

    Chen, Xingxing; Zhang, Zijian; Ding, Zicheng; Liu, Jun; Wang, Lixiang

    2016-08-22

    Conjugated polymers are essential for solution-processable organic opto-electronic devices. In contrast to the great efforts on developing new conjugated polymer backbones, research on developing side chains is rare. Herein, we report branched oligo(ethylene glycol) (OEG) as side chains of conjugated polymers. Compared with typical alkyl side chains, branched OEG side chains endowed the resulting conjugated polymers with a smaller π-π stacking distance, higher hole mobility, smaller optical band gap, higher dielectric constant, and larger surface energy. Moreover, the conjugated polymers with branched OEG side chains exhibited outstanding photovoltaic performance in polymer solar cells. A power conversion efficiency of 5.37 % with near-infrared photoresponse was demonstrated and the device performance could be insensitive to the active layer thickness.

  8. Keto-Functionalized Polymer Scaffolds As Versatile Precursors to Polymer Side Chain Conjugates.

    PubMed

    Liu, Jingquan; Li, Ronald C; Sand, Gregory J; Bulmus, Volga; Davis, Thomas P; Maynard, Heather D

    2013-01-01

    A new methacrylate monomer with a reactive ketone side-chain, 2-(4-oxo-pentanoate) ethyl methacrylate (PAEMA), was synthesized and subsequently polymerized by reversible addition-fragmentation chain transfer (RAFT) polymerization to give a polymer with a narrow molecular weight distribution (PDI = 1.25). The polymer was chain extended with poly(ethylene glycol methyl ether acrylate) (PEGMA) to yield a block copolymer. Aminooxy containing small molecules and oligoethylene glycol were conjugated to the ketone functionality of the side chain in high yields. Cytotoxicity of the oxime-linked tetra(ethylene glycol) polymer to mouse fibroblast cells was investigated; the polymer was found to be non-cytotoxic up to 1 mg/mL. The ease with which this polymer is functionalized, suggests that it may be useful in forming tailored polymeric medicines.

  9. Self-assembled conjugated polymer spheres as fluorescent microresonators

    PubMed Central

    Tabata, Kenichi; Braam, Daniel; Kushida, Soh; Tong, Liang; Kuwabara, Junpei; Kanbara, Takaki; Beckel, Andreas; Lorke, Axel; Yamamoto, Yohei

    2014-01-01

    Confinement of light inside an active medium cavity can amplify emission. Whispering gallery mode (WGM) is one of mechanisms that amplifies light effectively by confining it inside high-refractive-index microstructures, where light propagates along the circumference of a sphere via total internal reflection. Here we show that isolated single microspheres of 2–10 μm diameter, formed from self-assembly of π-conjugated alternating copolymers, display WGM photoemission induced by laser pumping. The wavelengths of the emission peaks depend sensitively on the sphere size, position of the excitation spot and refractive index of each polymer. The Q-factor increases with increasing sphere diameter and displays a linear correlation with the reciprocal radius, indicating that the small curvature increases the efficacy of the total internal reflection. WGM photoemission from π-conjugated polymer microspheres is unprecedented and may be of high technological impact since the microspheres fulfill the role of fluorophores, high-refractive-index media and resonators simultaneously, in addition to their simple fabrication process. PMID:25082187

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

    SciTech Connect

    Hayward, Ryan C.

    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.

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

    DOEpatents

    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.

  12. Making Glasses Conduct: Electrochemical Doping of Redox-Active Polymer Thin Films

    NASA Astrophysics Data System (ADS)

    Boudouris, Bryan

    Optoelectronically-active macromolecules have been established as promising materials in myriad organic electronic applications (e.g., organic field-effect transistors (OFETs) and organic photovoltaic (OPV) devices). To date, however, the majority of the work surrounding these materials has focused on materials with a great deal of conjugation along their macromolecular backbones and with varying degrees of crystalline structure. Here, we describe an emerging class of macromolecular charge conductors, radical polymers, that: (1) do not contain conjugation and (2) are completely amorphous glasses. Radical polymers contain non-conjugated macromolecular backbones and stable radical sites along the side chains of the electronically-active materials. In contrast to conjugated polymer systems, these materials conduct charge in the solid state through oxidation-reduction (redox) reactions along these pendant groups. Specifically, we demonstrate that controlling the chemical functionality of the pendant groups and the molecular mobility of the macromolecular backbones significantly impacts the charge transport ability of the pristine (i.e., not doped) radical polymers species. Through proper control of these crucial parameters, we show that radical polymers can have electrical conductivity and charge mobility values on par with commonly-used conjugated polymers. Importantly, we also highlight the ability to dope radical polymers with redox-active small molecule species. This doping, in turn, increases the electrical conductivity of the glassy radical polymer thin films in a manner akin to what is observed in traditional conjugated polymer systems. In this way, we establish a means by which to fabricate optically-transparent and colorless thin film glasses capable of conducting charge in a rather rapid manner. We anticipate that these fundamental insights will prove crucial in developing new transparent conducting layers for future electronic applications.

  13. Polymer enzyme conjugates as chiral ligands for sharpless dihydroxylation of alkenes in organic solvents.

    PubMed

    Konieczny, Stefan; Leurs, Melanie; Tiller, Joerg C

    2015-01-02

    Conjugates of enzymes and poly(2-methyloxazoline) were used as organosoluble amphiphilic polymer nanocontainers for dissolving osmate, thereby converting the enzymes into organosoluble artificial metalloenzymes. These were shown to catalyze the dihydroxylation of different alkenes with high enantioselectivity. The highest selectivities, found for osmate complexed with laccase polymer-enzyme conjugates (PECs), even exceed those of classical Sharpless catalysts.

  14. Site-Specific Zwitterionic Polymer Conjugates of a Protein Have Long Plasma Circulation.

    PubMed

    Bhattacharjee, Somnath; Liu, Wenge; Wang, Wei-Han; Weitzhandler, Isaac; Li, Xinghai; Qi, Yizhi; Liu, Jinyao; Pang, Yan; Hunt, Donald F; Chilkoti, Ashutosh

    2015-11-01

    Many proteins suffer from suboptimal pharmacokinetics (PK) that limit their utility as drugs. The efficient synthesis of polymer conjugates of protein drugs with tunable PK to optimize their in vivo efficacy is hence critical. We report here the first study of the in vivo behavior of a site-specific conjugate of a zwitterionic polymer and a protein. To synthesize the conjugate, we first installed an initiator for atom-transfer radical polymerization (ATRP) at the N terminus of myoglobin (Mb-N-Br). Subsequently, in situ ATRP was carried out in aqueous buffer to grow an amine-functionalized polymer from Mb-N-Br. The cationic polymer was further derivatized to two zwitterionic polymers by treating the amine groups of the cationic polymer with iodoacetic acid to obtain poly(carboxybetaine methacrylate) with a one-carbon spacer (PCBMA; C1 ), and sequentially with 3-iodopropionic acid and iodoacetic acid to obtain PCBMA(mix) with a mixture of C1 and C2 spacers. The Mb-N-PCBMA polymer conjugates had a longer in vivo plasma half-life than a PEG-like comb polymer conjugate of similar molecular weights (MW). The structure of the zwitterion plays a role in controlling the in vivo behavior of the conjugate, as the PCBMA conjugate with a C1 spacer had significantly longer plasma circulation than the conjugate with a mixture of C1 and C2 spacers.

  15. Preparation and characterization of gradient polymer films

    SciTech Connect

    Smith, S.C.

    1987-01-01

    Gradient polymers are multicomponent polymers whose chemical constitution varies with depth in the sample. Although these polymers may possess unique mechanical, optical, and barrier properties they remain relatively unexplored. This work is a study of the preparation of gradient polymers by sequential exposure of films to a diffusing monomer followed by electron beam irradiation. Initial experiments involved immersion of poly(vinyl chloride) (PVC) films in styrene or n-butyl methacrylate (BMA) for various time periods followed by irradiation with 1 or 10 megarads of accelerated electrons. A significant amount of poly(n-butyl methacrylate) (PBMA) formed in PVC/BMA systems, but little polystyrene could be found in the PVC/styrene films. A second set of experiments involved immersion of PVC and polyethylene (PE) films in BMA for 20, 40, 60, and 720 minutes followed by irradiation with 10 megarads of electrons. These films were then characterized using optical microscopy, quantitative transmission Fourier transform infrared spectroscopy (FTIR), and a depth profiling procedure based on quantitative attenuated total reflection (ATR) FTIR. It was concluded that the mechanism of PBMA formation in the polyethylene films was a result of events immediately following irradiation. Atmospheric oxygen diffusing into irradiated films trapped free radicals at the film surfaces. This was followed by storage in an evacuated desiccator where unintentional exposure to BMA vapor took place. This BMA reacted with free radicals that remained within the film cores, polymerizing to PBMA.

  16. Creating Ordered Antibody Arrays with Antibody-Polymer Conjugates

    NASA Astrophysics Data System (ADS)

    Dong, Xuehui; Obermeyer, Allie; Olsen, Bradley

    Antibodies are a category of functional proteins that play crucial roles in the immune system and have been widely applied in the area of cancer therapeutics, targeting delivery, signal detection, and sensors. Due to the extremely large size and lack of specific functional groups on the surface, it is challenging to functionalize antibodies and manipulate the ordered packing of antibodies in an array with high density and proper orientation, which is critical to achieve outstanding performance in materials. In this work, we demonstrate an efficient and facile approach for preparing antibody-polymer conjugates with two-step sequential ``click'' reaction to form antibody-polymer block copolymers. Highly ordered nanostructures are fabricated based on the principles of block copolymer self-assembly. The nanostructures are studied with both small angle X-ray scattering (SAXS) and transmission electron microscopy (TEM). Lamellae with alternating antibody domain and polymer domain are observed with an overall domain size of ~50 nm. The nanostructure not only increases the packing density and promotes proper orientation of the antibody, but also provides possible channel to facilitate substrate transportation and improves the stability of the antibody.

  17. Electronic interaction in composites of a conjugated polymer and carbon nanotubes: first-principles calculation and photophysical approaches

    PubMed Central

    Wéry, Jany; Duvail, Jean-Luc; Lefrant, Serge; Yaya, Abu; Ewels, Chris

    2015-01-01

    Summary The mechanisms that control the photophysics of composite films made of a semiconducting conjugated polymer (poly(paraphenylene vinylene), PPV) mixed with single-walled carbon nanotubes (SWNT) up to a concentration of 64 wt % are determined by using photoexcitation techniques and density functional theory. Charge separation is confirmed experimentally by rapid quenching of PPV photoluminescence and changes in photocurrent starting at relatively low concentrations of SWNT. Calculations predict strong electronic interaction between the polymer and the SWNT network when nanotubes are semiconducting. PMID:26171290

  18. Morphology in electrochemically grown conducting polymer films

    DOEpatents

    Rubinstein, I.; Gottesfeld, S.; Sabatani, E.

    1992-04-28

    A conducting polymer film with an improved space filling is formed on a metal electrode surface. A self-assembling monolayer is formed directly on the metal surface where the monolayer has a first functional group that binds to the metal surface and a second chemical group that forms a chemical bonding site for molecules forming the conducting polymer. The conducting polymer is then conventionally deposited by electrochemical deposition. In one example, a conducting film of polyaniline is formed on a gold electrode surface with an intermediate monolayer of p-aminothiophenol. 2 figs.

  19. Morphology in electrochemically grown conducting polymer films

    DOEpatents

    Rubinstein, Israel; Gottesfeld, Shimshon; Sabatani, Eyal

    1992-01-01

    A conducting polymer film with an improved space filling is formed on a metal electrode surface. A self-assembling monolayer is formed directly on the metal surface where the monolayer has a first functional group that binds to the metal surface and a second chemical group that forms a chemical bonding site for molecules forming the conducting polymer. The conducting polymer is then conventioonally deposited by electrochemical deposition. In one example, a conducting film of polyaniline is formed on a gold electrode surface with an intermediate monolayer of p-aminothiophenol.

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

    PubMed

    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.

  1. High Dielectric Constant Polymer Film Capacitors (PREPRINT)

    DTIC Science & Technology

    2010-02-01

    film, and the test of our first generation prototype capacitors . High-K Polymeric Dielectrics Commercial polypropylene (PP) capacitor film has a...1994). 2. Maurizio Rabuffi and Guido Picci, “Status Quo and Future Prospects for Metallized Polypropylene Energy Storage Capacitors ”, IEEE Trans...AFRL-RZ-WP-TP-2010-2126 HIGH DIELECTRIC CONSTANT POLYMER FILM CAPACITORS (PREPRINT) Shihai Zhang, Brian Zellers, Dean Anderson, Paul

  2. Design of hybrid conjugated polymer materials: 1) Novel inorganic/organic hybrid semiconductors and 2) Surface modification via grafting approaches

    NASA Astrophysics Data System (ADS)

    Peterson, Joseph J.

    synthesized and characterized, and the material is found to be a high MW, soluble blue emitter which shows a higher glass transition temperature and greater stability than a non-hybrid polymer. UV absorbance and fluorescence spectroscopy indicated some electronic interaction between the conjugated polymer and the cages, but they did not appear to be fully conjugated in the traditional sense. Chapter 4 describes the design, synthesis, and characterization of poly(fluorene) with o-carborane in the backbone. Profound changes in the behavior of the polymer, from its polymerization behavior to its emission characteristics, were observed and their origins are discussed. Experiments to explore the nature of the cage/polymer interactions were performed and possible applications which take advantage of the unique nature of the o-carborane hybrid polymer are explored and discussed. Hybrid conjugated polymer materials via grafting approaches to surfaces and surface modification are discussed starting in chapter 5. The synthesis of a dibromofluorene-based silane coupling agent for the surface functionalization of oxide surfaces is presented, and the surface directed Ni(0) dehalogenative polymerization of poly(dihexylfluorene) is explored. Chapter 6 focuses on the exploration of conjugated polymer/cellulose hybrid materials. Surface medication of cellulose materials with monomer-like anchor points is discussed. Grafting of the modified cellulose with conjugated polymers was explored and the grafting of three different repeat structures based on fluorene-, fluorenevinylene-, and fluoreneethynylene motifs were optimized to provide a general route to cellulose/conjugated polymer hybrid materials. Characterization and possible applications of such hybrid materials are discussed. Finally, chapter 7 is devoted to the simultaneous surface patterning and functionalization of poly(2-hydroxyethylmethacrylate) thin films using a silane infusion-based wrinkling technique. While not a conjugated

  3. Tuning hyperfine fields in conjugated polymers for coherent organic spintronics.

    PubMed

    Lee, Sang-Yun; Paik, Seo-Young; McCamey, Dane R; Yu, Justin; Burn, Paul L; Lupton, John M; Boehme, Christoph

    2011-02-23

    An appealing avenue for organic spintronics lies in direct coherent control of the spin population by means of pulsed electron spin resonance techniques. Whereas previous work has focused on the electrical detection of coherent spin dynamics, we demonstrate here the equivalence of an all-optical approach, allowing us to explore the influence of materials chemistry on the spin dynamics. We show that deuteration of the conjugated polymer side groups weakens the local hyperfine fields experienced by electron-hole pairs, thereby lowering the threshold for the resonant radiation intensity at which coherent coupling and spin beating occur. The technique is exquisitively sensitive to previously obscured material properties and offers a route to quantifying and tuning hyperfine fields in organic semiconductors.

  4. Multicolor Conjugated Polymer Dots for Biological Fluorescence Imaging

    PubMed Central

    Wu, Changfeng; Bull, Barbara; Szymanski, Craig; Christensen, Kenneth; McNeill, Jason

    2009-01-01

    Highly fluorescent conjugated polymer dots were developed for demanding applications such as fluorescence imaging in live cells. These nanoparticles exhibit small particle diameters, extraordinary fluorescence brightness, and excellent photostability. Single particle fluorescence imaging and kinetic studies indicate much higher emission rates (∼108 s-1) and little or no blinking of the nanoparticles as compared to typical results for single dye molecules and quantum dots. Analysis of single particle photobleaching trajectories reveals excellent photostability — as many as 109 or more photons emitted per nanoparticle prior to irreversible photobleaching. The superior figures of merit of these new fluorescent probes, together with the demonstration of cellular imaging, indicate their enormous potential for demanding fluorescence-based imaging and sensing applications such as high speed super-resolution single molecule/particle tracking and highly sensitive assays. PMID:19206410

  5. Hydrophobic conjugated microporous polymers for sorption of human serum albumin

    NASA Astrophysics Data System (ADS)

    Zheng, Chunli; Du, Miaomiao; Feng, Shanshan; Sun, Hanxue; Li, An; He, Chi; Zhang, TianCheng; Wang, Qiaorui; Wei, Wei

    2016-02-01

    This paper investigated the sorption of human serum albumin (HSA) from water by three kinds of conjugated microporous polymers (CMPs) with surface hydrophobicity and intrinsic porosity. It was found that the three CMPs captured HSA with fast sorption kinetics and good working capacity. Equilibrium was obtained at 80 min for all the tests, and the maximum sorption quantity (qm) ranged from 0.07 to 0.14 mg/mg. With the increase in the particle external surface area of the CMPs, a greater extent of HSA sorption was achieved. Moreover, promoting the dispersion of CMPs in HSA aqueous solution was also beneficial to the extraction. Attenuated Total Reflection Fourier Transform Infrared spectroscopy verified the interactions between the CMPs and the Nsbnd H, Cdbnd O, and Csbnd N groups of HSA. This paper might provide fundamental guidance for the practical application of CMPs to proteins separation and recovery.

  6. Theory of exciton transfer and diffusion in conjugated polymers

    SciTech Connect

    Barford, William; Tozer, Oliver Robert

    2014-10-28

    We describe a theory of Förster-type exciton transfer between conjugated polymers. The theory is built on three assumptions. First, we assume that the low-lying excited states of conjugated polymers are Frenkel excitons coupled to local normal modes, and described by the Frenkel-Holstein model. Second, we assume that the relevant parameter regime is ℏω < J, i.e., the adiabatic regime, and thus the Born-Oppenheimer factorization of the electronic and nuclear degrees of freedom is generally applicable. Finally, we assume that the Condon approximation is valid, i.e., the exciton-polaron wavefunction is essentially independent of the normal modes. The resulting expression for the exciton transfer rate has a familiar form, being a function of the exciton transfer integral and the effective Franck-Condon factors. The effective Franck-Condon factors are functions of the effective Huang-Rhys parameters, which are inversely proportional to the chromophore size. The Born-Oppenheimer expressions were checked against DMRG calculations, and are found to be within 10% of the exact value for a tiny fraction of the computational cost. This theory of exciton transfer is then applied to model exciton migration in conformationally disordered poly(p-phenylene vinylene). Key to this modeling is the assumption that the donor and acceptor chromophores are defined by local exciton ground states (LEGSs). Since LEGSs are readily determined by the exciton center-of-mass wavefunction, this theory provides a quantitative link between polymer conformation and exciton migration. Our Monte Carlo simulations indicate that the exciton diffusion length depends weakly on the conformation of the polymer, with the diffusion length increasing slightly as the chromophores became straighter and longer. This is largely a geometrical effect: longer and straighter chromophores extend over larger distances. The calculated diffusion lengths of ∼10 nm are in good agreement with experiment. The spectral

  7. Exploiting EPR in polymer drug conjugate delivery for tumor targeting.

    PubMed

    Modi, Sweta; Prakash Jain, Jay; Domb, A J; Kumar, Neeraj

    2006-01-01

    Treatment of tumor tissue without affecting normal cells has always been formidable task for drug delivery scientists and this task is effectively executed by polymer drug conjugate (PDC) delivery. The novelty of this concept lies in the utilization of a physical mechanism called enhanced permeability and retention (EPR) for targeting tumors. EPR is a physiological phenomenon that is customary for fast growing tumor and solves the problem of targeting the miscreant tissue. PDCs offer added advantages of reduced deleterious effects of anticancer drugs and augmentation of its formulation capability (e.g. Solubility). There are now at least eleven PDCs that have entered phase I/II/III clinical trial as anticancer drugs. PDCs once entered into the tumor tissue, taking advantage of EPR, are endocytosed into the cell either by simple or receptor mediated endocytosis. Various polymeric carriers have been used with hydrolyzable linker arm for conjugation with bioactive moiety. The hydrolyzable linkages of PDC are broken down by acid hydrolyses of lysosomes and releases the drug. High concentrations of the chemotherapeutic agent are maintained near the nucleus, the target site. Passive targeting by PDCs is due to the physiological event of EPR, which is becoming one of the major thrust areas for targeting solid tumors.

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

    NASA Astrophysics Data System (ADS)

    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

    2016-12-01

    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.

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

    PubMed

    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.

  10. Pentafluorophenyl ester-functionalized phosphorylcholine polymers: preparation of linear, two-arm, and grafted polymer-protein conjugates.

    PubMed

    McRae, Samantha; Chen, Xiangji; Kratz, Katrina; Samanta, Debasis; Henchey, Elizabeth; Schneider, Sallie; Emrick, Todd

    2012-07-09

    Novel pentafluorophenyl (PFP)-ester-functionalized phosphorylcholine (PC) polymers of different architectures were prepared and conjugated to lysozyme as a model protein. Linear and two-arm poly(2-methacryloyloxyethyl phosphorylcholine) (polyMPC) structures containing PFP functionality at the chain-end were prepared by atom transfer radical polymerization (ATRP) from novel initiators. Additional conjugates were prepared from phosphorylcholine-substituted cyclooctene (PC-COE) polymers containing PFP-ester bearing comonomers. The polymer-protein conjugates were characterized by HPLC, FPLC, and DLS and were seen to retain most (~80% or greater) of their native enzymatic activity. Pharmacokinetic profiles of the polymer-protein conjugates were studied in mice and found to increase the circulation half-life compared with lysozyme alone.

  11. Thiophene polymer semiconductors for organic thin-film transistors.

    PubMed

    Ong, Beng S; Wu, Yiliang; Li, Yuning; Liu, Ping; Pan, Hualong

    2008-01-01

    Printed organic thin-film transistors (OTFTs) have received great interests as potentially low-cost alternative to silicon technology for application in large-area, flexible, and ultra-low-cost electronics. One of the critical materials for TFTs is semiconductor, which has a dominant impact on the transistor properties. We review here the structural studies and design of thiophene-based polymer semiconductors with respect to solution processability, ambient stability, molecular self-organization, and field-effect transistor properties for OTFT applications. We show that through judicial monomer design, delicately controlled pi-conjugation, and strategically positioned pendant side-chain distribution, novel solution-processable thiophene polymer semiconductors with excellent self-organization ability to form extended lamellar pi-stacking orders can be developed. OTFTs using semiconductors of this nature processed in ambient conditions have provided excellent field-effect transistor properties.

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

    PubMed

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

    2014-06-01

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

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

    PubMed

    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.

  14. Low dose ionizing radiation detection using conjugated polymers

    SciTech Connect

    Silva, E.A.B.; Borin, J.F.; Nicolucci, P.; Graeff, C.F.O.; Netto, T. Ghilardi; Bianchi, R.F.

    2005-03-28

    In this work, the effect of gamma radiation on the optical properties of poly[2-methoxy-5-(2{sup '}-ethylhexyloxy)-p-phenylenevinylene] (MEH-PPV) is studied. The samples were irradiated at room temperature with different doses from 0 Gy to 152 Gy using a {sup 60}Co gamma ray source. For thin films, significant changes in the UV-visible spectra were only observed at high doses (>1 kGy). In solution, shifts in absorption peaks are observed at low doses (<10 Gy), linearly dependent on dose. The shifts are explained by conjugation reduction, and possible causes are discussed. Our results indicate that MEH-PPV solution can be used as a dosimeter adequate for medical applications.

  15. Photorefractivity in liquid crystals doped with a soluble conjugated polymer.

    SciTech Connect

    Niemczyk, M. P.; Svec, W. A.; Wasielewski, M. R.; Wiederrecht, G. P.

    1999-07-07

    Photoconductive polymers are doped into liquid crystals to create a new mechanism for space-charge field formation in photorefractive liquid crystal composites. The composites contain poly(2,5-bis(2{prime}-ethylhexyloxy)-1,4-phenylenevinylene) (BEH-PPV) and the electron acceptor N,N{prime}-dioctyl-1,4:5,8-naphthalenediimide, NI. Using asymmetric energy transfer (beam coupling) measurements that are diagnostic for the photorefractive effect, the direction of beam coupling as a function of grating fringe spacing inverts at a spacing of 5.5 {micro}m. We show that the inversion is due to a change in the dominant mechanism for space-charge field formation. At small fringe spacings, the space-charge field is formed by ion diffusion in which the photogenerated anion is the more mobile species. At larger fringe spacings, the polarity of the space charge field inverts due to dominance of a charge transport mechanism in which photogenerated holes are the most mobile species due to hole migration along the BEH-PPV chains coupled with interchain hole hopping. Control experiments are presented, which use composites that can access only one of the two charge transport mechanisms. The results show that charge migration over long distances leading to enhanced photorefractive effects can be obtained using conjugated polymers dissolved in liquid crystals.

  16. Hydrochromic conjugated polymers for human sweat pore mapping

    PubMed Central

    Lee, Joosub; Pyo, Minkyeong; Lee, Sang-hwa; Kim, Jaeyong; Ra, Moonsoo; Kim, Whoi-Yul; Park, Bum Jun; Lee, Chan Woo; Kim, Jong-Man

    2014-01-01

    Hydrochromic materials have been actively investigated in the context of humidity sensing and measuring water contents in organic solvents. Here we report a sensor system that undergoes a brilliant blue-to-red colour transition as well as ‘Turn-On’ fluorescence upon exposure to water. Introduction of a hygroscopic element into a supramolecularly assembled polydiacetylene results in a hydrochromic conjugated polymer that is rapidly responsive (<20 μs), spin-coatable and inkjet-compatible. Importantly, the hydrochromic sensor is found to be suitable for mapping human sweat pores. The exceedingly small quantities (sub-nanolitre) of water secreted from sweat pores are sufficient to promote an instantaneous colorimetric transition of the polymer. As a result, the sensor can be used to construct a precise map of active sweat pores on fingertips. The sensor technology, developed in this study, has the potential of serving as new method for fingerprint analysis and for the clinical diagnosis of malfunctioning sweat pores. PMID:24781362

  17. Engineered Polymer-Transferrin Conjugates as Self-Assembling Targeted Drug Delivery Systems.

    PubMed

    Makwana, Hiteshri; Mastrotto, Francesca; Magnusson, Johannes Pall; Sleep, Darrell; Hay, Joanna; Nicholls, Karl J; Allen, Stephanie; Alexander, Cameron

    2017-03-28

    Polymer-protein conjugates can be engineered to self-assemble into discrete and well-defined drug delivery systems which combine the advantages of receptor targeting and controlled drug release. We designed specific conjugates of the iron-binding and transport protein, transferrin (Tf), to combine the advantages of this serum-stable protein as a targeting agent for cancer cells with self-assembling polymers to act as carriers of cytotoxic drugs. Tf variants were expressed with cysteine residues at sites spanning different regions of the protein surface and the polymer conjugates grown from these variants were compared with polymer conjugates grown from non-selectively derivatised sites on native Tf. The resulting synthetic biopolymer hybrids were evaluated for self-assembly properties, size and topology, ability to carry an anti-cancer drug (paclitaxel) and cytotoxicity with and without a drug payload in a representative human colon cancer cell line. The results demonstrated that the engineered Tf variant polymer conjugates formed better-defined self-assembled nanoparticles than the non-selectively derivatised conjugates and showed greater efficacy in paclitaxel delivery. A polymer conjugate grown from a specific Tf variant, S415C was found to be taken up rapidly into cancer cells expressing the Tf-receptor, and, while tolerated well by cells in the absence of drugs, was as cytotoxic as free paclitaxel when loaded with the drug. Importantly, the S415C conjugate polymer was not the most active variant in Tf-receptor binding, suggesting that the nanoscale self-assembly of the polymer-protein hybrid is also a key factor in delivery efficacy. The data overall suggest new design rules for polymer-biopolymer hybrids and therapeutic delivery systems which include engineering specific residues for conjugation which mediate nanoscale assembly as well as control of ligand-receptor interactions to target specific cell types.

  18. Charge separation and transport in conjugated-polymer/semiconductor-nanocrystal composites studied by photoluminescence quenching and photoconductivity

    SciTech Connect

    Greenham, N.C.; Peng, X.; Alivisatos, A.P.

    1996-12-01

    We study the processes of charge separation and transport in composite materials formed by mixing cadmium selenide or cadmium sulfide nanocrystals with the conjugated polymer poly(2-methoxy,5-(2{prime}-ethyl)-hexyloxy-{ital p}-phenylenevinylene) (MEH-PPV). When the surface of the nanocrystals is treated so as to remove the surface ligand, we find that the polymer photoluminescence is quenched, consistent with rapid charge separation at the polymer/nanocrystal interface. Transmission electron microscopy of these quantum-dot/conjugated-polymer composites shows clear evidence for phase segregation with length scales in the range 10{endash}200 nm, providing a large area of interface for charge separation to occur. Thin-film photovoltaic devices using the composite materials show quantum efficiencies that are significantly improved over those for pure polymer devices, consistent with improved charge separation. At high concentrations of nanocrystals, where both the nanocrystal and polymer components provide continuous pathways to the electrodes, we find quantum efficiencies of up to 12{percent}. We describe a simple model to explain the recombination in these devices, and show how the absorption, charge separation, and transport properties of the composites can be controlled by changing the size, material, and surface ligands of the nanocrystals. {copyright} {ital 1996 The American Physical Society.}

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

    PubMed

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

    2014-05-20

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

  20. Mesoscale morphologies in polymer thin films.

    SciTech Connect

    Ramanathan, M.; Darling, S. B.

    2011-06-01

    In the midst of an exciting era of polymer nanoscience, where the development of materials and understanding of properties at the nanoscale remain a major R&D endeavor, there are several exciting phenomena that have been reported at the mesoscale (approximately an order of magnitude larger than the nanoscale). In this review article, we focus on mesoscale morphologies in polymer thin films from the viewpoint of origination of structure formation, structure development and the interaction forces that govern these morphologies. Mesoscale morphologies, including dendrites, holes, spherulites, fractals and honeycomb structures have been observed in thin films of homopolymer, copolymer, blends and composites. Following a largely phenomenological level of description, we review the kinetic and thermodynamic aspects of mesostructure formation outlining some of the key mechanisms at play. We also discuss various strategies to direct, limit, or inhibit the appearance of mesostructures in polymer thin films as well as an outlook toward potential areas of growth in this field of research.

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

    PubMed

    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 (<4 nm) PDFDT layers without using any receptor additives. The sensing mechanism was confirmed by cyclic voltammetry, hydrogen/fluorine nuclear magnetic resonance, and UV/visible absorption spectroscopy. PDFDT-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.

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

    NASA Astrophysics Data System (ADS)

    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

  3. Antimicrobial polymer films for food packaging

    NASA Astrophysics Data System (ADS)

    Concilio, S.; Piotto, S.; Sessa, L.; Iannelli, P.; Porta, A.; Calabrese, E. C.; Galdi, M. R.; Incarnato, L.

    2012-07-01

    New antimicrobial polymeric systems were realized introducing new antimicrobial azo compounds in PP and LDPE matrices. The polymeric materials containing different percentage of azo compounds were mold-casted and the obtained film were tested in vitro against Gram+ and Gram- bacteria and fungi. These results hold promise for the fabrication of bacteria-resistant polymer films by means of simple melt processing with antimicrobial azo-dyes.

  4. "Bio"-macromolecules: polymer-protein conjugates as emerging scaffolds for therapeutics.

    PubMed

    Borchmann, Dorothee E; Carberry, Tom P; Weck, Marcus

    2014-01-01

    Polymer-protein conjugates are biohybrid macromolecules derived from covalently connecting synthetic polymers with polypeptides. The resulting materials combine the properties of both worlds: chemists can engineer polymers to stabilize proteins, to add functionality, or to enhance activity; whereas biochemists can exploit the specificity and complexity that Nature has bestowed upon its macromolecules. This has led to a wealth of applications, particularly within the realm of biomedicine. Polymer-protein conjugation has expanded to include scaffolds for drug delivery, tissue engineering, and microbial inhibitors. This feature article reflects upon recent developments in the field and discusses the applications of these hybrids from a biomaterials standpoint.

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

    SciTech Connect

    Barford, William; Marcus, Max

    2014-10-28

    We describe a theory of linear optical transitions in conjugated polymers. The theory is based on three assumptions. The first is that the low-lying excited states of conjugated polymers are Frenkel excitons coupled to local normal modes, described by the Frenkel-Holstein model. Second, we assume that the relevant parameter regime is ℏω ≪ J, i.e., the adiabatic regime, and thus the Born-Oppenheimer factorization of the electronic and nuclear degrees of freedom is generally applicable. Finally, we assume that the Condon approximation is valid, i.e., the exciton-polaron wavefunction is essentially independent of the normal modes. Using these assumptions we derive an expression for an effective Huang-Rhys parameter for a chain (or chromophore) of N monomers, given by S(N) = S(1)/IPR, where S(1) is the Huang-Rhys parameter for an isolated monomer. IPR is the inverse participation ratio, defined by IPR = (∑{sub n}|Ψ{sub n}|{sup 4}){sup −1}, where Ψ{sub n} is the exciton center-of-mass wavefunction. Since the IPR is proportional to the spread of the exciton center-of-mass wavefunction, this is a key result, as it shows that S(N) decreases with chain length. As in molecules, in a polymer S(N) has two interpretations. First, ℏωS(N) is the relaxation energy of an excited state caused by its coupling to the normal modes. Second, S(N) appears in the definition of an effective Franck-Condon factor, F{sub 0v}(N) = S(N){sup v}exp ( − S(N))/v! for the vth vibronic manifold. We show that the 0 − 0 and 0 − 1 optical intensities are proportional to F{sub 00}(N) and F{sub 01}(N), respectively, and thus the ratio of the 0 − 1 to 0 − 0 absorption and emission intensities are proportional to S(N). These analytical results are checked by extensive DMRG calculations and found to be generally valid, particularly for emission. However, for large chain lengths higher-lying quasimomentum exciton states become degenerate with the lowest vibrational excitation of the

  6. Polarons in π-Conjugated Polymers: Anderson or Landau?

    PubMed

    Barford, William; Marcus, Max; Tozer, Oliver Robert

    2016-02-04

    Using both analytical expressions and the density matrix renormalization group method, we study the fully quantized disordered Holstein model to investigate the localization of charges and excitons by vibrational or torsional modes-i.e., the formation of polarons-in conformationally disordered π-conjugated polymers. We identify two distinct mechanisms for polaron formation, namely Anderson localization via disorder (causing the formation of Anderson polarons) and self-localization by self-trapping via normal modes (causing the formation of Landau polarons). We identify the regimes where either description is more valid. The key distinction between Anderson and Landau polarons is that for the latter the particle wave function is a strong function of the normal coordinates, and hence the "vertical" and "relaxed" wave functions are different. This has theoretical and experimental consequences for Landau polarons. Theoretically, it means that the Condon approximation is not valid, and so care needs to be taken when evaluating transition rates. Experimentally, it means that the self-localization of the particle as a consequence of its coupling to the normal coordinates may lead to experimental observables, e.g., ultrafast fluorescence depolarization. We apply these ideas to poly(p-phenylenevinylene). We show that the high frequency C-C bond oscillation only causes Landau polarons for a very narrow parameter regime; generally we expect disorder to dominate and Anderson polarons to be a more applicable description. Similarly, for the low frequency torsional fluctuations we show that Anderson polarons are expected for realistic parameters.

  7. Polarity engineering of conjugated polymers by variation of chemical linkages connecting conjugated backbones.

    PubMed

    Yun, Hui-Jun; Choi, Hyun Ho; Kwon, Soon-Ki; Kim, Yun-Hi; Cho, Kilwon

    2015-03-18

    The fine tuning of the dominant polarity in polymer semiconductors is a key issue for high-performance organic complementary circuits. In this paper, we demonstrate a new methodology for addressing this issue in terms of molecular design. In an alternating conjugated donor-acceptor copolymer system, we systematically engineered the chemical linkages that connect the aromatic units in donor moieties. Three donor moieties, thiophene-vinylene-thiophene (TVT), thiophene-acetylene-thiophene (TAT), and thiophene-cyanovinylene-thiophene (TCNT), were combined with an acceptor moiety, thienoisoindigo (TIID), and finally, three novel TIID-based copolymers were synthesized: PTIID-TVT, PTIID-TAT, and PTIID-TCNT. We found that the vinylene, acetylene, and cyanovinylene linkages decisively affect the energy structure, molecular orbital delocalization, microstructure, and, most importantly, the dominant polarity of the polymers. The vinylene-linked PTIID-TVT field-effect transistors (FETs) exhibited intrinsic hole and electron mobilities of 0.12 and 1.5 × 10(-3) cm(2) V(-1 )s(-1), respectively. By contrast, the acetylene-linked PTIID-TAT FETs exhibited significantly improved intrinsic hole and electron mobilities of 0.38 and 0.03 cm(2) V(-1) s(-1), respectively. Interestingly, cyanovinylene-linked PTIID-TCNT FETs exhibited reverse polarity, with hole and electron mobilities of 0.07 and 0.19 cm(2) V(-1) s(-1). As a result, the polarity balance, which is quantified as the electron/hole mobility ratio, was dramatically tuned from 0.01 to 2.7. Our finding demonstrates a new methodology for the molecular design of high-performance organic complementary circuits.

  8. Photovoltaic properties of polymer films

    NASA Astrophysics Data System (ADS)

    Reucroft, P. J.; Ullal, H.

    1980-03-01

    The effect of metal electrode and film thickness on the photovoltaic energy conversion efficiency in (1:1) mole ratio films of poly (N-vinylcarbazole) (PVK) and 2,4,7-trinitrofluorenone (TNF) has been investigated. Low work function metals increase the Schottky barrier height which leads to increases in the photovoltaic energy conversion efficiency. A ten-fold decrease in film thickness produces a thousand-fold increase in photovoltaic energy conversion efficiency. A theoretical model which assumes that the photovoltaic current is limited by Child's law predicts photovoltaic efficiencies which are in good agreement with the measured efficiencies.

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

    PubMed Central

    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

    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. PMID:27929115

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

    PubMed

    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.

  11. Dewetting of thin-film polymers.

    PubMed

    Saulnier, F; Raphaël, E; De Gennes, P-G

    2002-12-01

    In this paper we present a theoretical model for the dewetting of ultrathin polymer films. Assuming that the shear-thinning properties of these films can be described by a Cross-type constitutive equation, we analyze the front morphology of the dewetting film, and characterize the time evolution of the dry region radius, and of the rim height. Different regimes of growth are expected, depending on the initial film thickness, and on the power-law index involved in the constitutive equation. In the thin-films regime, the dry radius and the rim height obey power-law time dependences. We then compare our predictions with the experimental results obtained by Debrégeas et al. [Phys. Rev. Lett. 75, 3886 (1995)] and by Reiter [Phys. Rev. Lett. 87, 186101 (2001)].

  12. Inorganic-polymer-derived dielectric films

    DOEpatents

    Brinker, C. Jeffrey; Keefer, Keith D.; Lenahan, Patrick M.

    1987-01-01

    A method of coating a substrate with a thin film of a polymer of predetermined porosity comprises depositing the thin film on the substrate from a non-gelled solution comprising at least one hydrolyzable metal alkoxide of a polymeric network forming cation, water, an alcohol compatible with the hydrolysis and the polymerization of the metal alkoxide, and an acid or a base, prior to depositing the film, controlling the structure of the polymer for a given composition of the solution exclusive of the acid or base component and the water component, (a) by adjusting each of the water content, the pH, and the temperature to obtain the desired concentration of alkoxide, and then adjusting the time of standing of the solution prior to lowering the temperature of the solution, and (b) lowering the temperature of the solution after the time of standing to about 15 degrees C. or lower to trap the solution in a state in which, after the depositing step, a coating of the desired porosity will be obtained, and curing the deposited film at a temperature effective for curing whereby there is obtained a thin film of a polymer of a predetermined porosity and corresponding pore size on the substrate.

  13. Affinity separation using an Fv antibody fragment-"smart" polymer conjugate.

    PubMed

    Fong, Robin B; Ding, Zhongli; Hoffman, Allan S; Stayton, Patrick S

    2002-08-05

    Poly(N-isopropylacrylamide), or PNIPAAm, is considered a "smart" polymer because it sharply precipitates when heated above a critical temperature, about 32 degrees C in water, and redissolves when cooled. Conjugates made of PNIPAAm and IgG antibodies also exhibit the same critical temperature behavior. Interestingly, antigens that are complexed with these conjugates can also be phase-separated along with the conjugates. In this work, we conjugated PNIPAAm for the first time to the immunoglobulin Fv fragment, the smallest fragment of an antibody that still retains the antigenic affinity of the whole antibody. For our studies, we used an Fv fragment that strongly binds hen egg white lysozyme (HEL). The purified Fv fragment-polymer conjugate precipitated at the same temperature as did the pure polymer. After addition of the conjugate to a mixture containing HEL and after thermal separation of the conjugate at 37 degrees C, the amount of HEL in solution was reduced by as much as 80%. We were able to demonstrate the reversibility of the separation through three cycles of precipitation and dissolution. It was also possible to recover free HEL by thermal separation of the conjugate in the presence of an eluant, 50 mM diethylamine. The conjugate can then be recycled for second use. In conclusion, immunoseparations can be performed using smart polymer conjugates made with just the variable domains of an antibody. Unlike whole antibodies, fragments of antibodies can be produced in Escherichia coli, allowing easier genetic engineering of the antibody and tailoring of the conjugate.

  14. Multifunctional polymer-metal nanocomposites via direct chemical reduction by conjugated polymers.

    PubMed

    Xu, Ping; Han, Xijiang; Zhang, Bin; Du, Yunchen; Wang, Hsing-Lin

    2014-03-07

    Noble metal nanoparticles (MNPs) have attracted continuous attention due to their promising applications in chemistry, physics, bioscience, medicine and materials science. As an alternative to conventional solution chemistry routes, MNPs can be directly synthesized through a conjugated polymer (CP) mediated technique utilizing the redox chemistry of CPs to chemically reduce the metal ions and modulate the size, morphology, and structure of the MNPs. The as-prepared multifunctional CP-MNP nanocomposites have shown application potentials as highly sensitive surface enhanced Raman spectroscopy (SERS) substrates, effective heterogeneous catalysts for organic synthesis and electrochemistry, and key components for electronic and sensing devices. In this tutorial review, we begin with a brief introduction to the chemical nature and redox properties of CPs that enable the spontaneous reduction of noble metal ions to form MNPs. We then focus on recent progress in control over the size, morphology and structure of MNPs during the conjugated polymer mediated syntheses of CP-MNP nanocomposites. Finally, we highlight the multifunctional CP-MNP nanocomposites toward their applications in sensing, catalysis, and electronic devices.

  15. Enhancing performing characteristics of organic semiconducting films by improved solution processing

    SciTech Connect

    Bazan, Guillermo C; Moses, Daniel; Peet, Jeffrey; Heeger, Alan J

    2014-05-13

    Improved processing methods for enhanced properties of conjugated polymer films are disclosed, as well as the enhanced conjugated polymer films produced thereby. Addition of low molecular weight alkyl-containing molecules to solutions used to form conjugated polymer films leads to improved photoconductivity and improvements in other electronic properties. The enhanced conjugated polymer films can be used in a variety of electronic devices, such as solar cells and photodiodes.

  16. Enhancing performance characteristics of organic semiconducting films by improved solution processing

    DOEpatents

    Bazan, Guillermo C [Santa Barbara, CA; Heeger, Alan J [Santa Barbara, CA; Moses, Daniel [Santa Barbara, CA; Peet, Jeffrey [Goleta, CA

    2013-09-25

    Improved processing methods for enhanced properties of conjugated polymer films are disclosed, as well as the enhanced conjugated polymer films produced thereby. Addition of low molecular weight alkyl-containing molecules to solutions used to form conjugated polymer films leads to improved photoconductivity and improvements in other electronic properties. The enhanced conjugated polymer films can be used in a variety of electronic devices, such as solar cells and photodiodes.

  17. Enhancing performance characteristics of organic semiconducting films by improved solution processing

    DOEpatents

    Bazan, Guillermo C; Mikhailovsky, Alexander; Moses, Daniel; Nguyen, Thuc-Quyen; Peet, Jeffrey; Soci, Cesare

    2012-11-27

    Improved processing methods for enhanced properties of conjugated polymer films are disclosed, as well as the enhanced conjugated polymer films produced thereby. Addition of low molecular weight alkyl-containing molecules to solutions used to form conjugated polymer films leads to improved photoconductivity and improvements in other electronic properties. The enhanced conjugated polymer films can be used in a variety of electronic devices, such as solar cells and photodiodes.

  18. Strong Composition Effects in All-Polymer Phototransistors with Bulk Heterojunction Layers of p-type and n-type Conjugated Polymers.

    PubMed

    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 (<10 wt %). The photosensing experiments revealed that the photosensivity of all-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.

  19. Z-Group ketone chain transfer agents for RAFT polymer nanoparticle modification via hydrazone conjugation

    PubMed Central

    Bandyopadhyay, Saibal; Xia, Xin; Maiseiyeu, Andrei; Mihai, Georgeta; Rajagopalan, Sanjay

    2012-01-01

    A ketal-containing trithiocarbonyl compound has been synthesized and characterized as a chain transfer agent (CTA) in Reversible Addition Fragmentation Transfer (RAFT) polymerization. The ketal functionality does not interfere with RAFT polymerization of acrylate monomers, which proceeds as previously reported to yield macro-CTA polymers and block co-polymers. Post-polymerization ketal cleavage revealed ketone functionality at the polar terminus of an amphiphilic block co-polymer. Hydrazone-formation was facile in both organic solution as well as in aqueous buffer where polymer nanoparticle assemblies were formed, indicating a conjugation/end-functionalization yield of 40–50%. Conjugation was verified with fluorescein, biotin and Gd-DOTA derivatives, and though the trithiocarbonate linkage is hydrolytically labile, we observed stable conjugation for several days at pH 7.4. and 37°C. As expected, streptavidin binding to biotinylated polymer micelles was observed, and size-change based relaxivity increases were observed when Gd-DOTA hydrazide was conjugated to polymer micelles. Cell-uptake of fluorescently labeled polymer micelles was also readily tracked by FACS and fluorescence microscopy. These polymer derivatives demonstrate a range of potential theranostic/biotechnological applications for this conveniently accessible keto-CTA, which include ligand-based nanoparticle targeting and fluorescent/MR nanoparticle contrast agents. PMID:23148126

  20. Unsubstituted Benzodithiophene-Based Conjugated Polymers for High-Performance Organic Field-Effect Transistors and Organic Solar Cells.

    PubMed

    Chen, Weichao; Xiao, Manjun; Han, Liangliang; Zhang, Jidong; Jiang, Huanxiang; Gu, Chuantao; Shen, Wenfei; Yang, Renqiang

    2016-08-03

    Unsubstituted benzo[1,2-b:4,5-b']dithiophene (BDT) was used to construct a high-performance conjugated polymer with 5,6-difluoro-4,7-bis[4-(2-octyldodecyl)thiophene-2-yl]benzo[c][1,2,5] thiadiazole (DTFFBT), named PBDT-DTFFBT. The polymer shows the low-lying highest occupied molecular orbital (HOMO) energy level (-5.40 eV) and a broad absorption spectra with strong vibronic absorption peak. Pure polymer films exhibit good crystallinity and edge-on orientation, partially attributed to the BDT units without any side chains, and as a result, the corresponding thin-film transistor showed excellent hole mobility over 1 cm(2) V(-1) s(-1). Interestingly, a well-distributed nanofibrillar polymer aggregation with face-on orientation was obviously formed when blending with PC71BM, which was in favor of the charge transportation. Consequently, the bulk heterojunction polymer solar cells based on the blends showed high power conversion efficiency of 9.29% with large short-current density (14.56 mA cm(-2)) and high fill factor (0.751) without any process additives or thermal annealing.

  1. Porous Polyolefin Films via Polymer Blends

    NASA Astrophysics Data System (ADS)

    Macosko, Chris

    Porous polymer films have broad application including battery separators, membrane supports and filters. Polyolefins are attractive for these applications because of their solvent resistance, low electrical and thermal conductivity, easy fabrication and cost. We will describe fabrication of porous films using cocontinuous blends of a polyolefin with another polymer which can be readily removed with a solvent. Methods to image and control the cocontinuous morphology will be presented.Bell, J. R., K. Chang, C. R. Lopez-Barron, C. W. Macosko, and D. C. Morse, ''Annealing of cocontinuous polymer blends: effect of block copolymer molecular weight and architecture,'' Macromolecules 43, 5024-5032 (2010).Lopez-Barron, C. R., and C. W. Macosko, ''Direct measurement of interface anisotropy of bicontinuous structures via 3D image analysis,'' Langmuir 26, 14284-14293 (2010).Trifkovic, M., A. T. Hedegaard, K. Huston, M. Sheikhzadeh, and C. W. Macosko, ''Porous films via PE/PEO cocontinuous blends,'' Macromolecules 45, 6036-6044 (2012).Hedegaard, A.T., L.L. Gu and C. W. Macosko, ``Effect of Extensional Viscosity on Cocontinuity of Immiscible Polymer Blends'' J. Rheol. 59, 1397-1417 (2015).

  2. Theoretical analysis of single molecule spectroscopy lineshapes of conjugated polymers

    NASA Astrophysics Data System (ADS)

    Devi, Murali

    Conjugated Polymers(CPs) exhibit a wide range of highly tunable optical properties. Quantitative and detailed understanding of the nature of excitons responsible for such a rich optical behavior has significant implications for better utilization of CPs for more efficient plastic solar cells and other novel optoelectronic devices. In general, samples of CPs are plagued with substantial inhomogeneous broadening due to various sources of disorder. Single molecule emission spectroscopy (SMES) offers a unique opportunity to investigate the energetics and dynamics of excitons and their interactions with phonon modes. The major subject of the present thesis is to analyze and understand room temperature SMES lineshapes for a particular CP, called poly(2,5-di-(2'-ethylhexyloxy)-1,4-phenylenevinylene) (DEH-PPV). A minimal quantum mechanical model of a two-level system coupled to a Brownian oscillator bath is utilized. The main objective is to identify the set of model parameters best fitting a SMES lineshape for each of about 200 samples of DEH-PPV, from which new insight into the nature of exciton-bath coupling can be gained. This project also entails developing a reliable computational methodology for quantum mechanical modeling of spectral lineshapes in general. Well-known optimization techniques such as gradient descent, genetic algorithms, and heuristic searches have been tested, employing an L2 measure between theoretical and experimental lineshapes for guiding the optimization. However, all of these tend to result in theoretical lineshapes qualitatively different from experimental ones. This is attributed to the ruggedness of the parameter space and inadequateness of the L2 measure. On the other hand, when the dynamic reduction of the original parameter space to a 2-parameter space through feature searching and visualization of the search space paths using directed acyclic graphs(DAGs), the qualitative nature of the fitting improved significantly. For a more

  3. Membranes and Films from Polymers.

    ERIC Educational Resources Information Center

    Blumberg, Avrom A.

    1986-01-01

    Provides background information on polymeric films and membranes including production methods, special industrial and medical applications, laboratory preparation, and an experimental investigation of a porous cellulose acetate membrane. Presents a demonstration to distinguish between high- and low-density polyethylene. (JM)

  4. MISSE 6 Polymer Film Tensile Experiment

    NASA Technical Reports Server (NTRS)

    Miller, Sharon K. R.; Dever, Joyce A.; Banks, Bruce A.; Waters, Deborah L.; Sechkar, Edward; Kline, Sara

    2010-01-01

    The Polymer Film Tensile Experiment (PFTE) was flown as part of Materials International Space Station Experiment 6 (MISSE 6). The purpose of the experiment was to expose a variety of polymer films to the low Earth orbital environment under both relaxed and tension conditions. The polymers selected are those commonly used for spacecraft thermal control and those under consideration for use in spacecraft applications such as sunshields, solar sails, and inflatable and deployable structures. The dog-bone shaped samples of polymers that were flown were exposed on both the side of the MISSE 6 Passive Experiment Container (PEC) that was facing into the ram direction (receiving atomic oxygen, ultraviolet (UV) radiation, ionizing radiation, and thermal cycling) and the wake facing side (which was supposed to have experienced predominantly the same environmental effects except for atomic oxygen which was present due to reorientation of the International Space Station). A few of the tensile samples were coated with vapor deposited aluminum on the back and wired to determine the point in the flight when the tensile sample broke as recorded by a change in voltage that was stored on battery powered data loggers for post flight retrieval and analysis. The data returned on the data loggers was not usable. However, post retrieval observation and analysis of the samples was performed. This paper describes the preliminary analysis and observations of the polymers exposed on the MISSE 6 PFTE.

  5. Effect of polymer aggregation on the open circuit voltage in organic photovoltaic cells: aggregation-induced conjugated polymer gel and its application for preventing open circuit voltage drop.

    PubMed

    Kim, Bong-Gi; Jeong, Eun Jeong; Park, Hui Joon; Bilby, David; Guo, L Jay; Kim, Jinsang

    2011-03-01

    To investigate the structure-dependent aggregation behavior of conjugated polymers and the effect of aggregation on the device performance of conjugated polymer photovoltaic cells, new conjugated polymers (PVTT and CN-PVTT) having the same regioregularity but different intermolecular packing were prepared and characterized by means of UV-vis spectroscopy and atomic force microscopy (AFM). Photovoltaic devices were prepared with these polymers under different polymer-aggregate conditions. Polymer aggregation induced by thermal annealing increases the short circuit current but provides no advantage in the overall power conversion efficiency because of a decrease in the open circuit voltage. The device fabricated from a pre-aggregated polymer suspension, acquired from ultrasonic agitation of a conjugated polymer gel, showed enhanced performance because of better phase separation and reduced recombination between polymer/PCBM.

  6. Dendritic polymer imaging systems for the evaluation of conjugate uptake and cleavage.

    PubMed

    Krüger, Harald R; Nagel, Gregor; Wedepohl, Stefanie; Calderón, Marcelo

    2015-03-07

    Fluorescent turn-on probes combined with polymers have a broad range of applications, e.g. for intracellular sensing of ions, small molecules, or DNA. In the field of polymer therapeutics, these probes can be applied to extend the in vitro characterization of novel conjugates beyond cytotoxicity and cellular uptake studies. This is particularly true in cases in which polymer conjugates contain drugs attached by cleavable linkers. Better information on the intracellular linker cleavage and drug release would allow a faster evaluation and optimization of novel polymer therapeutic concepts. We therefore developed a fluorescent turn-on probe that enables direct monitoring of pH-mediated cleavage processes over time. This is achieved by exploiting the fluorescence resonance energy transfer (FRET) between two dyes that have been coupled to a dendritic polymer. We demonstrate the use of this probe to evaluate polymer uptake and intracellular release of cargo in a cell based microplate assay that is suitable for high throughput screening.

  7. Thin Polymer Films Containing Carbon Nanostructures

    NASA Astrophysics Data System (ADS)

    Paszkiewicz, S.; Piesowicz, E.; Irska, I.; Roslaniec, Z.; Szymczyk, A.; Pawelec, I.

    2016-05-01

    Within the framework of the presented paper, the research experiments were conducted on the preparation and characterization of polymer thin films containing carbon nanotubes, graphene derivatives and hybrid systems of both CNTs/graphene derivatives, in which condensation polymers constituted the matrix. The use of in situ synthesis allowed to obtain nanocomposites with a high degree of homogeneity, which is a key issue for further industrial applications, while the analysis of the physical properties of the obtained materials showed effect of the addition of carbon nanotubes and graphene derivatives on their structure, barrier properties and thermal and electrical conductivity.

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

    PubMed

    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.

  9. Novel Effects of Compressed CO2 Molecules on Structural Ordering and Charge Transport in Conjugated Poly(3-hexylthiophene) Thin Films

    SciTech Connect

    Jiang, Naisheng; Sendogdular, Levent; Sen, Mani; Endoh, Maya K.; Koga, Tadanori; Fukuto, Masafumi; Akgun, Bulent; Satija, Sushil K.; Nam, Chang-Yong

    2016-10-06

    We report the effects of compressed CO2 molecules as a novel plasticization agent for poly(3- hexylthiophene) (P3HT) conjugated polymer thin films. In-situ neutron reflectivity experiment demonstrated the excess sorption of CO2 molecules in the P3HT thin films (about 40 nm in thickness) at low pressure (P = 8.2 MPa) under the isothermal condition of T = 36 °C, which is far below the polymer bulk melting point. The results evidenced that these CO2 molecules accelerated the crystallization process of the polymer on the basis of ex-situ grazing incidence Xray diffraction measurements after drying the films via rapid depressurization to atmospheric pressure: not only the out-of-plane lamellar ordering of the backbone chains but also intra-plane π-π stacking of the side chains were significantly improved, when compared to those in the control P3HT films subjected to conventional thermal annealing (at T = 170 °C). Electrical measurements elucidated that the CO2-annealed P3HT thin films exhibited enhanced charge carrier mobility along with decreased background charge carrier concentration and trap density compared to those in the thermally annealed counterpart. This is attributed to the CO2-induced increase in polymer chain mobility that can drive the detrapping of molecular oxygen and healing of conformational defects in the polymer thin film. Given the universality of the excess sorption of CO2regardless of the type of polymers, the present findings suggest that the CO2 annealing near the critical point can be useful as a robust processing strategy for improving structural and electrical characteristics of other semiconducting conjugated polymers and related systems such as polymer: fullerene bulk heterojunction films.tion films.

  10. Developing conjugated polymers with high electron affinity by replacing a C-C unit with a B←N unit.

    PubMed

    Dou, Chuandong; Ding, Zicheng; Zhang, Zijian; Xie, Zhiyuan; Liu, Jun; Wang, Lixiang

    2015-03-16

    The key parameters of conjugated polymers are lowest unoccupied molecular orbital (LUMO) and highest occupied molecular orbital (HOMO) energy levels. Few approaches can simultaneously lower LUMO and HOMO energy levels of conjugated polymers to a large extent (>0.5 eV). Disclosed herein is a novel strategy to decrease both LUMO and HOMO energy levels of conjugated polymers by about 0.6 eV through replacement of a C-C unit by a B←N unit. The replacement makes the resulting polymer transform from an electron donor into an electron acceptor, and is proven by fluorescence quenching experiments and the photovoltaic response. This work not only provides an effective approach to tune the LUMO/HOMO energy levels of conjugated polymers, but also uses organic boron chemistry as a new toolbox to develop conjugated polymers with high electron affinity for polymer optoelectronic devices.

  11. Suppression of quantum dot blinking in DTT-doped polymer films

    PubMed Central

    Antelman, Josh; Ebenstein, Yuval; Dertinger, Thomas; Michalet, Xavier; Weiss, Shimon

    2009-01-01

    In this report we evaluate the emission properties of single quantum dots embedded in a thin, thiol containing polymer film. We report the suppression of quantum dot blinking leading to a continuous photon flux from both organic and water soluble quantum dots and demonstrate their application as robust fluorescent point sources for ultrahigh resolution localization. In addition, we apply the polymer coating to cell samples immunostained with antibody conjugated QDs and show that fluorescence intensity from the polymer embedded cells shows no sign of degradation after 67 hours of continuous excitation. The reported thin polymer film coating may prove advantageous for immuno-cyto/histo-chemistry as well as for the fabrication of quantum dot containing devices requiring a reliable and stable photon source (including a single photon source) or stable charge characteristics while maintaining intimate contact between the quantum dot and the surrounding matrix. PMID:20161096

  12. Direct Light-Driven Water Oxidation by a Ladder-Type Conjugated Polymer Photoanode

    PubMed Central

    2015-01-01

    A conjugated polymer known for high stability (poly[benzimidazobenzophenanthroline], coded as BBL) is examined as a photoanode for direct solar water oxidation. In aqueous electrolyte with a sacrificial hole acceptor (SO32–), photoelectrodes show a morphology-dependent performance. Films prepared by a dispersion-spray method with a nanostructured surface (feature size of ∼20 nm) gave photocurrents up to 0.23 ± 0.02 mA cm–2 at 1.23 VRHE under standard simulated solar illumination. Electrochemical impedance spectroscopy reveals a constant flat-band potential over a wide pH range at +0.31 VNHE. The solar water oxidation photocurrent with bare BBL electrodes is found to increase with increasing pH, and no evidence of semiconductor oxidation was observed over a 30 min testing time. Characterization of the photo-oxidation reaction suggests H2O2 or •OH production with the bare film, while functionalization of the interface with 1 nm of TiO2 followed by a nickel–cobalt catalyst gave solar photocurrents of 20–30 μA cm–2, corresponding with O2 evolution. Limitations to photocurrent production are discussed. PMID:26576469

  13. Improving photo-stability of conjugated polymer MEH-PPV embedded in solid matrices by purification of the matrix polymer

    NASA Astrophysics Data System (ADS)

    Tian, Yuxi; Sheinin, Vladimir; Kulikova, Olga; Mamardashvili, Nugzar; Scheblykin, Ivan G.

    2014-04-01

    For single molecule spectroscopy (SMS), molecules under study are usually immobilized in a polymer matrix e.g. poly(methyl methacrylate). We show a very significant improvement of the conjugated polymer MEH-PPV photo-stability and decrease of the luminescence impurities concentration when the matrix is purified. We identify benzoyl peroxide (a common radical initiator) as a possible oxidizing agent which residuals in the polymer matrix destroy MEH-PPV. These results show that purification and selection of a matrix obtained by radical-free synthetic technique are of great importance for SMS as well as other technologies using polymer matrices as hosts for light-emitting materials.

  14. High-Temperature Capacitor Polymer Films

    NASA Astrophysics Data System (ADS)

    Tan, Daniel; Zhang, Lili; Chen, Qin; Irwin, Patricia

    2014-12-01

    Film capacitor technology has been under development for over half a century to meet various applications such as direct-current link capacitors for transportation, converters/inverters for power electronics, controls for deep well drilling of oil and gas, direct energy weapons for military use, and high-frequency coupling circuitry. The biaxially oriented polypropylene film capacitor remains the state-of-the-art technology; however, it is not able to meet increasing demand for high-temperature (>125°C) applications. A number of dielectric materials capable of operating at high temperatures (>140°C) have attracted investigation, and their modifications are being pursued to achieve higher volumetric efficiency as well. This paper highlights the status of polymer dielectric film development and its feasibility for capacitor applications. High-temperature polymers such as polyetherimide (PEI), polyimide, and polyetheretherketone were the focus of our studies. PEI film was found to be the preferred choice for high-temperature film capacitor development due to its thermal stability, dielectric properties, and scalability.

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

    PubMed

    Narasimha, Karnati; Jayakannan, Manickam

    2014-11-12

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

  16. Exciton diffusion and dissociation in conjugated polymer/fullerene blends and heterostructures

    NASA Astrophysics Data System (ADS)

    Haugeneder, A.; Neges, M.; Kallinger, C.; Spirkl, W.; Lemmer, U.; Feldmann, J.; Scherf, U.; Harth, E.; Gügel, A.; Müllen, K.

    1999-06-01

    We investigate the exciton dynamics in composite systems of conjugated polymers and fullerene molecules by photoluminescence (PL) and femtosecond transient absorption experiments. In solid mixtures (blends) we find a strong concentration-dependent quenching of the polymer PL. This is attributed to an efficient electron transfer (ET) from the photoexcited conjugated polymer to the fullerene. The ET dynamics is directly monitored by measuring the transient stimulated emission of the conjugated polymer. The transfer rate depends linearly on the C60 concentration and ranges between (66 ps)-1 and (5 ps)-1 for concentrations from 0.5% to 5%. This dependence is in accordance with an exciton diffusion process occurring prior to the ET. The exciton diffusion length in the conjugated polymer is directly determined by measuring the PL quenching in well-defined heterostructures comprising a self-assembled fullerene monolayer and a thin spin-coated polymer layer of variable thickness. From these measurements we infer a value of 14 nm for the exciton diffusion length in ladder-type poly (p-phenylene). Our results are of direct relevance for further optimization of polymer photovoltaic devices.

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

    PubMed

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

    2011-09-01

    This paper describes the preparation and characterization of polymer-protein conjugates composed of a synthetic triblock copolymer with a central polypropylene oxide (PPO) block and two terminal polyethylene oxide (PEO) segments, Pluronic F-127, and the antibacterial enzyme lysozyme attached to the telechelic groups of the PEO chains. Covalent conjugation of lysozyme proceeded via reductive amination of aldehyde functionalized PEO blocks (CHO-Pluronic) and the amine groups of the lysine residues in the protein. SDS-PAGE gel electrophoresis together with MALDI-TOF mass spectrometry analysis revealed formation of conjugates of one or two lysozyme molecules per Pluronic polymer chain. The conjugated lysozyme showed antibacterial activity towards Bacillus subtilis. Analysis with a quartz crystal microbalance with dissipation revealed that Pluronic-lysozyme conjugates adsorb in a brush conformation on a hydrophobic gold-coated quartz surface. X-ray photoelectron spectroscopy indicated surface coverage of 32% by lysozyme when adsorbed from a mixture of unconjugated Pluronic and Pluronic-lysozyme conjugate (ratio 99:1) and of 47% after adsorption of 100% Pluronic-lysozyme conjugates. Thus, bifunctional brushes were created, possessing both anti-adhesive activity due to the polymer brush, combined with the antibacterial activity of lysozyme. The coating having a lower degree of lysozyme coverage proved to be more bactericidal.

  18. Influence of backbone rigidness on single chain conformation of thiophene-based conjugated polymers.

    PubMed

    Hu, Zhongjian; Liu, Jianhua; Simón-Bower, Lauren; Zhai, Lei; Gesquiere, Andre J

    2013-04-25

    Structural order of conjugated polymers at different length scales directs the optoelectronic properties of the corresponding materials; thus it is of critical importance to understand and control conjugated polymer morphology for successful application of these materials in organic optoelectronics. Herein, with the aim of probing the dependence of single chain folding properties on the chemical structure and rigidness of the polymer backbones, single molecule fluorescence spectroscopy was applied to four thiophene-based conjugated polymers. These include regioregular poly(3-hexylthiophene) (RR-P3HT), poly(2,5-bis(3-tetradecylthiophen-2-yl)thieno[3,2-b]thiophene) (PBTTT-14), poly(2,5-bis(3-tetradecylthiophen-2-yl)thiophene-2-yl)thiophen-2-ylthiazolo[5,4-d]thiazole) (PTzQT-12), and poly(3,3-didodecylquaterthiophene)] (PQT-12). Our previous work has shown that RR-P3HT and PBTTT-14 polymer chains fold in their nanostructures, whereas PQT-12 and PTzQT-12 do not fold in their nanostructures. At the single molecule level, it was found that RR-P3HT single chains almost exclusively fold into loosely and strongly aggregated conformations, analogous to the folding properties in nanostructures. PQT-12 displays significant chain folding as well, but only into loosely aggregated conformations, showing an absence of strongly aggregated polymer chains. PBTTT-14 exhibits a significant fraction of rigid polymer chain. The findings made for single molecules of PQT-12 and PBTTT-14 are thus in contrast with the observations made in their corresponding nanostructures. PTzQT-12 appears to be the most rigid and planar conjugated polymer of these four polymers. However, although the presumably nonfolding polymers PQT-12 and PTzQT-12 exhibit less folding than RR-P3HT, there is still a significant occurrence of chain folding for these polymers at the single molecule level. These results suggest that the folding properties of conjugated polymers can be influenced by the architecture of the

  19. Protein polymer conjugates: improving the stability of hemoglobin with poly(acrylic acid).

    PubMed

    Thilakarathne, Vindya; Briand, Victoria A; Zhou, Yuxiang; Kasi, Rajeswari M; Kumar, Challa V

    2011-06-21

    The synthesis, characterization, and evaluation of a novel polymer-protein conjugate are reported here. The covalent conjugation of high-molecular weight poly(acrylic acid) (PAA) to the lysine amino groups of met-hemoglobin (Hb) resulted in the covalent conjugation of Hb to PAA (Hb-PAA conjugate), as confirmed by dialysis and electrophoresis studies. The retention of native-like structure of Hb in Hb-PAA was established from Soret absorption, circular dichroism studies, and the redox activity of the iron center in Hb-PAA. The peroxidase-like activities of the Hb-PAA conjugate further confirmed the retention of Hb structure and biological activity. Thermal denaturation of the conjugate was investigated by differential scanning calorimetry and steam sterilization studies. The Hb-PAA conjugate indicated an improved denaturation temperature (T(d)) when compared to that of the unmodified Hb. One astonishing observation was that polymer conjugation significantly enhanced the Hb-PAA storage stability at room temperature. After 120 h of storage at room temperature in phosphate-buffered saline (PBS) at pH 7.4, for example, Hb-PAA retained 90% of its initial activity and unmodified Hb retained <60% of its original activity under identical conditions of buffer, pH, and temperature. Our conjugate demonstrates the key role of polymers in enhancing Hb stability via a very simple, efficient, general route. Water-swollen, lightly cross-linked, stable Hb-polymer nanogels of 100-200 nm were produced quickly and economically by this approach for a wide variety of applications.

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

    NASA Astrophysics Data System (ADS)

    Shu, Jessica Yo

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

  1. Germanium films by polymer-assisted deposition

    DOEpatents

    Jia, Quanxi; Burrell, Anthony K.; Bauer, Eve; Ronning, Filip; McCleskey, Thomas Mark; Zou, Guifu

    2013-01-15

    Highly ordered Ge films are prepared directly on single crystal Si substrates by applying an aqueous coating solution having Ge-bound polymer onto the substrate and then heating in a hydrogen-containing atmosphere. A coating solution was prepared by mixing water, a germanium compound, ethylenediaminetetraacetic acid, and polyethyleneimine to form a first aqueous solution and then subjecting the first aqueous solution to ultrafiltration.

  2. The pH-dependent and enzymatic release of cytarabine from hydrophilic polymer conjugates.

    PubMed

    Pola, R; Janoušková, O; Etrych, T

    2016-10-20

    Cytarabine is one of the most efficient drugs in the treatment of hematological malignancies. In this work, we describe the synthesis and characterization of two different polymer conjugates of cytarabine that were designed for the controlled release of cytarabine within the leukemia cells. Reactive copolymers of N-(2-hydroxypropyl)methacrylamide (HPMA) and 3-(3-methacrylamidopropa-noyl)thiazolidine-2-thione) or 3-(Nmethacryloylglycyl-phenylalanylleucylglycyl)thiazolidine-2-thione were used in the study as reactive polymer precursors for reaction with cytarabine. The enzymatic release of cytarabine from the conjugate containing a GFLG spacer utilizing cathepsin B was verified. In addition to enzymolysis, the pH-dependent hydrolysis of cytarabine from both copolymers was also confirmed. Approximately 40 % and 20 % of the drug was released by spontaneous hydrolysis at pH 7.4 within 72 h from the polymer conjugates with the GFLG and beta-Ala spacers, respectively. At pH 6.0, the spontaneous hydrolysis slowed down, and less than 10 % of the drug was liberated within 72 h. The results of the cytotoxicity evaluation of the polymer conjugates in vitro against various cell lines showed that the cytotoxicity of the polymer conjugates is approximately three times lower in comparison to free cytarabine.

  3. A Porphyrin-Based Conjugated Polymer for Highly Efficient In Vitro and In Vivo Photothermal Therapy.

    PubMed

    Guo, Bing; Feng, Guangxue; Manghnani, Purnima Naresh; Cai, Xiaolei; Liu, Jie; Wu, Wenbo; Xu, Shidang; Cheng, Xiamin; Teh, Cathleen; Liu, Bin

    2016-12-01

    Conjugated polymers have been increasingly studied for photothermal therapy (PTT) because of their merits including large absorption coefficient, facile tuning of exciton energy dissipation through nonradiative decay, and good therapeutic efficacy. The high photothermal conversion efficiency (PCE) is the key to realize efficient PTT. Herein, a donor-acceptor (D-A) structured porphyrin-containing conjugated polymer (PorCP) is reported for efficient PTT in vitro and in vivo. The D-A structure introduces intramolecular charge transfer along the backbone, resulting in redshifted Q band, broadened absorption, and increased extinction coefficient as compared to the state-of-art porphyrin-based photothermal reagent. Through nanoencapsulation, the dense packing of a large number of PorCP molecules in a single nanoparticle (NP) leads to favorable nonradiative decay, good photostability, and high extinction coefficient of 4.23 × 10(4) m(-1) cm(-1) at 800 nm based on porphyrin molar concentration and the highest PCE of 63.8% among conjugated polymer NPs. With the aid of coloaded fluorescent conjugated polymer, the cellular uptake and distribution of the PorCP in vitro can be clearly visualized, which also shows effective photothermal tumor ablation in vitro and in vivo. This research indicates a new design route of conjugated polymer-based photothermal therapeutic materials for potential personalized theranostic nanomedicine.

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

    PubMed

    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.

  5. DNA-SMART: Biopatterned Polymer Film Microchannels for Selective Immobilization of Proteins and Cells.

    PubMed

    Schneider, Ann-Kathrin; Nikolov, Pavel M; Giselbrecht, Stefan; Niemeyer, Christof M

    2017-02-22

    A novel SMART module, dubbed "DNA-SMART" (DNA substrate modification and replication by thermoforming) is reported, where polymer films are premodified with single-stranded DNA capture strands, microthermoformed into 3D structures, and postmodified with complementary DNA-protein conjugates to realize complex biologically active surfaces within microfluidic devices. As a proof of feasibility, it is demonstrated that microchannels presenting three different proteins on their inner curvilinear surface can be used for selective capture of cells under flow conditions.

  6. Understanding the relationship between molecular order and charge transport properties in conjugated polymer based organic blend photovoltaic devices.

    PubMed

    Wood, Sebastian; Kim, Jong Soo; James, David T; Tsoi, Wing C; Murphy, Craig E; Kim, Ji-Seon

    2013-08-14

    We report a detailed characterization of the thin film morphology of all-polymer blend devices by applying a combined analysis of physical, chemical, optical, and charge transport properties. This is exemplified by considering a model system comprising poly(3-hexylthiophene) (P3HT) and poly(9,9-dioctylfluorene-co-benzothiadiazole) (F8BT). We show that the interactions between the two conjugated polymer components can be controlled by pre-forming the P3HT into highly ordered nanowire structures prior to blending with F8BT, and by varying the molecular weight of the F8BT. As a result, it is possible to produce films containing highly ordered P3HT with hole mobilities enhanced by three orders of magnitude over the pristine blends. Raman spectroscopy under resonant excitation conditions is used to probe the molecular order of both P3HT and F8BT phases within the blend films and these morphological studies are complemented by measurements of photocurrent generation. The resultant increase in photocurrent is associated with the enhanced charge carrier mobilities. The complementary analytical method demonstrated here is applicable to a wide range of polymer blend systems for all applications where the relationships between morphology and device performance are of interest.

  7. Conjugated polymers containing diketopyrrolopyrrole units in the main chain

    PubMed Central

    Rabindranath, A Raman; Zhang, Kai; Zhu, Yu

    2010-01-01

    Summary Research activities in the field of diketopyrrolopyrrole (DPP)-based polymers are reviewed. Synthetic pathways to monomers and polymers, and the characteristic properties of the polymers are described. Potential applications in the field of organic electronic materials such as light emitting diodes, organic solar cells and organic field effect transistors are discussed. PMID:20978619

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

    PubMed

    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.

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

    PubMed Central

    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

  10. Remarkable enhancement of charge carrier mobility of conjugated polymer field-effect transistors upon incorporating an ionic additive.

    PubMed

    Luo, Hewei; Yu, Chenmin; Liu, Zitong; Zhang, Guanxin; Geng, Hua; Yi, Yuanping; Broch, Katharina; Hu, Yuanyuan; Sadhanala, Aditya; Jiang, Lang; Qi, Penglin; Cai, Zhengxu; Sirringhaus, Henning; Zhang, Deqing

    2016-05-01

    Organic semiconductors with high charge carrier mobilities are crucial for flexible electronic applications. Apart from designing new conjugated frameworks, different strategies have been explored to increase charge carrier mobilities. We report a new and simple approach to enhancing the charge carrier mobility of DPP-thieno[3,2-b]thiophene-conjugated polymer by incorporating an ionic additive, tetramethylammonium iodide, without extra treatments into the polymer. The resulting thin films exhibit a very high hole mobility, which is higher by a factor of 24 than that of thin films without the ionic additive under the same conditions. On the basis of spectroscopic grazing incidence wide-angle x-ray scattering and atomic force microscopy studies as well as theoretical calculations, the remarkable enhancement of charge mobility upon addition of tetramethylammonium iodide is attributed primarily to an inhibition of the torsion of the alkyl side chains by the presence of the ionic species, facilitating a more ordered lamellar packing of the alkyl side chains and interchain π-π interactions.

  11. Remarkable enhancement of charge carrier mobility of conjugated polymer field-effect transistors upon incorporating an ionic additive

    PubMed Central

    Luo, Hewei; Yu, Chenmin; Liu, Zitong; Zhang, Guanxin; Geng, Hua; Yi, Yuanping; Broch, Katharina; Hu, Yuanyuan; Sadhanala, Aditya; Jiang, Lang; Qi, Penglin; Cai, Zhengxu; Sirringhaus, Henning; Zhang, Deqing

    2016-01-01

    Organic semiconductors with high charge carrier mobilities are crucial for flexible electronic applications. Apart from designing new conjugated frameworks, different strategies have been explored to increase charge carrier mobilities. We report a new and simple approach to enhancing the charge carrier mobility of DPP-thieno[3,2-b]thiophene–conjugated polymer by incorporating an ionic additive, tetramethylammonium iodide, without extra treatments into the polymer. The resulting thin films exhibit a very high hole mobility, which is higher by a factor of 24 than that of thin films without the ionic additive under the same conditions. On the basis of spectroscopic grazing incidence wide-angle x-ray scattering and atomic force microscopy studies as well as theoretical calculations, the remarkable enhancement of charge mobility upon addition of tetramethylammonium iodide is attributed primarily to an inhibition of the torsion of the alkyl side chains by the presence of the ionic species, facilitating a more ordered lamellar packing of the alkyl side chains and interchain π-π interactions. PMID:27386541

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

    NASA Astrophysics Data System (ADS)

    Repenko, Tatjana; Kuehne, Alexander J. C.

    2015-10-01

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

  13. Hot Hole Transfer Increasing Polaron Yields in Hybrid Conjugated Polymer/PbS Blends.

    PubMed

    Strein, Elisabeth; deQuilettes, Dane W; Hsieh, Stephen T; Colbert, Adam E; Ginger, David S

    2014-01-02

    We use quasi-steady-state photoinduced absorption (PIA) to study charge generation in blends of poly(3-hexylthiophene-2,5-diyl) (P3HT) with PbS nanocrystal quantum dots as a function of excitation energy. We find that, per photon absorbed, the yield of photogenerated holes present on the conjugated polymer increases with pump energy, even at wavelengths where only the quantum dots absorb. We interpret this result as direct evidence for transfer of hot holes in these conjugated polymer/quantum dot blends. These results help understand the operation of hybrid organic/inorganic photovoltaics.

  14. Drug conjugation to cyclic peptide-polymer self-assembling nanotubes.

    PubMed

    Blunden, Bianca M; Chapman, Robert; Danial, Maarten; Lu, Hongxu; Jolliffe, Katrina A; Perrier, Sébastien; Stenzel, Martina H

    2014-09-26

    We show for the first time how polymeric nanotubes (NTs) based on self-assembled conjugates of polymers and cyclic peptides can be used as an efficient drug carrier. RAPTA-C, a ruthenium-based anticancer drug, was conjugated to a statistical co-polymer based on poly(2-hydroxyethyl acrylate) (pHEA) and poly(2-chloroethyl methacrylate) (pCEMA), which formed the shell of the NTs. Self-assembly into nanotubes (length 200-500 nm) led to structures exhibiting high activity against cancer cells.

  15. The Role of Morphology and Electronic Chain Aggregation on the Optical Gain Properties of Semiconducting Conjugated Polymers

    NASA Astrophysics Data System (ADS)

    Lampert, Zachary Evan

    Conjugated polymers (CPs) are a novel class of materials that exhibit the optical and electrical properties of semiconductors while still retaining the durability and processability of plastics. CPs are also intrinsically 4-level systems with high luminescence quantum efficiencies making them particularly attractive as organic gain media for solid-state laser applications. However, before CPs can emerge as a commercially available laser technology, a more comprehensive understanding of the morphological dependence of the photophysics is required. In this thesis, the morphology and chain conformation dependence of amplified spontaneous emission (ASE) and optical gain in thin films of poly[2-methoxy-5-(2'-ethylhexyloxy)-p-phenylene vinylene] (MEH-PPV) was investigated. By changing the chemical nature of the solvent from which films were cast, as well as the temperature at which films were annealed, CP films with different morphologies, and hence different degrees of interchain interactions were achieved. Contrary to the common perception that polymer morphology plays a decisive role in determining the ASE behavior of thin CP films, we found that chromophore aggregation and degree of conformational order have minimal impact on optical gain. In fact, experimental results indicated that an extremely large fraction of interchain aggregate species and/or exciton dissociating defects are required to significantly alter the optical properties and suppress stimulated emission. These results are pertinent to the fabrication and optimization of an electrically pumped laser device, as improvements in charge carrier mobility through controlled increases in chain aggregation may provide a viable means of optimizing injection efficiency without significantly degrading optical gain. To offset charge-induced absorption losses under electrical pumping, and to enable the use of more compact and economical sources under optical pumping, conjugated polymers exhibiting low lasing

  16. Reactions of brominated naphthalene diimide with bis(tributylstannyl)acetylene: a simple approach for conjugated polymers and versatile coupling intermediates.

    PubMed

    Alvey, Paul M; Iverson, Brent L

    2012-06-01

    A new synthetic approach to 1,4,5,8-naphthalenetetracarboxylic diimide (NDI) containing materials and conjugates is described. A simple one-step Stille coupling procedure is used to create either novel alkyne-linked NDI polymers or a new stannylated diyne synthetic building block that provides a flexible approach to new NDI conjugates and polymers.

  17. Scanning Tunneling Microscopy analysis of space-exposed polymer films

    NASA Technical Reports Server (NTRS)

    Kalil, Carol R.; Young, Philip R.

    1993-01-01

    The characterization of the surface of selected space-exposed polymer films by Scanning Tunneling Microscopy (STM) is reported. Principles of STM, an emerging new technique for materials analysis, are reviewed. The analysis of several films which received up to 5.8 years of low Earth orbital (LEO) exposure onboard the NASA Long Duration Exposure Facility (LDEF) is discussed. Specimens included FEP Teflon thermal blanket material, Kapton film, and several experimental polymer films. Ultraviolet and atomic oxygen-induced crazing and erosion are described. The intent of this paper is to demonstrate how STM is enhancing the understanding of LEO space environmental effects on polymer films.

  18. Influence of Energetic Disorder on Exciton Lifetime and Photoluminescence Efficiency in Conjugated Polymers.

    PubMed

    Rörich, Irina; Mikhnenko, Oleksandr V; Gehrig, Dominik; Blom, Paul W M; Crăciun, N Irina

    2017-02-16

    Using time-resolved photoluminescence (TRPL) spectroscopy the exciton lifetime in a range of conjugated polymers is investigated. For poly(p-phenylenevinylene) (PPV)-based derivatives and a polyspirobifluorene copolymer (PSBF) we find that the exciton lifetime is correlated with the energetic disorder. Better ordered polymers exhibit a single exponential PL decay with exciton lifetimes of a few hundred picoseconds, whereas polymers with a larger degree of disorder show multiexponential PL decays with exciton lifetimes in the nanosecond regime. These observations are consistent with diffusion-limited exciton quenching at nonradiative recombination centers. The measured PL decay time reflects the time that excitons need to diffuse toward these quenching sites. Conjugated polymers with large energetic disorder and thus longer exciton lifetime also exhibit a higher photoluminescence quantum yield due to the slower exciton diffusion toward nonradiative quenching sites.

  19. Dendritic polymer imaging systems for the evaluation of conjugate uptake and cleavage

    NASA Astrophysics Data System (ADS)

    Krüger, Harald R.; Nagel, Gregor; Wedepohl, Stefanie; Calderón, Marcelo

    2015-02-01

    Fluorescent turn-on probes combined with polymers have a broad range of applications, e.g. for intracellular sensing of ions, small molecules, or DNA. In the field of polymer therapeutics, these probes can be applied to extend the in vitro characterization of novel conjugates beyond cytotoxicity and cellular uptake studies. This is particularly true in cases in which polymer conjugates contain drugs attached by cleavable linkers. Better information on the intracellular linker cleavage and drug release would allow a faster evaluation and optimization of novel polymer therapeutic concepts. We therefore developed a fluorescent turn-on probe that enables direct monitoring of pH-mediated cleavage processes over time. This is achieved by exploiting the fluorescence resonance energy transfer (FRET) between two dyes that have been coupled to a dendritic polymer. We demonstrate the use of this probe to evaluate polymer uptake and intracellular release of cargo in a cell based microplate assay that is suitable for high throughput screening.Fluorescent turn-on probes combined with polymers have a broad range of applications, e.g. for intracellular sensing of ions, small molecules, or DNA. In the field of polymer therapeutics, these probes can be applied to extend the in vitro characterization of novel conjugates beyond cytotoxicity and cellular uptake studies. This is particularly true in cases in which polymer conjugates contain drugs attached by cleavable linkers. Better information on the intracellular linker cleavage and drug release would allow a faster evaluation and optimization of novel polymer therapeutic concepts. We therefore developed a fluorescent turn-on probe that enables direct monitoring of pH-mediated cleavage processes over time. This is achieved by exploiting the fluorescence resonance energy transfer (FRET) between two dyes that have been coupled to a dendritic polymer. We demonstrate the use of this probe to evaluate polymer uptake and intracellular

  20. Nanoscale imaging of nonequilibrium polymer films

    NASA Astrophysics Data System (ADS)

    King, John; Granick, Steve

    2015-03-01

    In recent years there have been exciting advances in sub-diffraction limited imaging based on fluorescence microscopy. While most applications of super-resolution microscopy focus on static biological imaging, we are interested in extending these techniques to the study of polymer dynamics. To this end, we couple stimulated emission depletion (STED) with spectroscopic detection, relying on spectral features of fluorescence emission to serve as the imaging contrast agent. We aim to adapt fluorescent dyes responsive to environmental properties (polarity, mobility, current, temperature, ect.) to STED imaging. Using the fluorescent spectral response as a contrast agent allows for nanoscopic environments to be directly imaged without the need for specific labeling. Rapid acquisition of images allows for slow dynamic processes in nonequilibrium polymer films to be imaged in real time. We demonstrate the power of super-resolution spectroscopic imaging by directly imaging several topical problems in materials science.

  1. Exciton dynamics in conjugated polymer photovoltaics: Steady-state and time-resolved optical spectroscopy

    NASA Astrophysics Data System (ADS)

    Chasteen, Stephanie V.

    The performance of organic photovoltaics is severely limited by poor exciton dissociation and charge transport due in part to high rates of exciton recombination and low charge mobilities in polymers. This challenge can be partially overcome through the use of blended and layered heterojunctions. Such morphologies offer multiple exciton dissociation sites and separate charge pathways, thus limiting exciton recombination, and allowing for thicker, more absorbing, polymer films. I have performed photovoltaic device characterization and time-resolved and steady-state photoluminescence on a variety of donor-acceptor heterojunction. I have used these methods to understand excited state dynamics and how they affect device performance. As hole-transporters I use a derivative of poly-phenylene-vinylene (M3EH-PPV) and poly-3-hexylthiophene (P3HT). As electron-transporters I use the metal oxide titanium dioxide (TiO2), the electron-transporter CN-PPV, and a fullerene derivative (PCBM). These materials are layered and blended together to form donor-acceptor heterojunctions. All heterojunctions result in enhanced device performance, and 1:4 M3EH-PPV:PCBM resulted in the highest efficiencies. M3EH-PPV emission is characterized by single-chain excitations, and the decay is dominated by short components of 0.20 and 0.45 ns. CN-ether-PPV is dominated by interchain excited state species---ie., excimers---with a decay time of 14.0 ns. The broken conjugation imposed by the ether group affect the excited state, resulting in an excited state species that is particularly vulnerable to quenching. This has important ramifications for material design. Hole-transporting polymers blended and layered with CN-ether-PPV have high currents (Jsc up to 3.3 mA/cm2) and good quenching relative to CN-ether-PPV (˜90%) due to charge separation and generation, respectively. Hole-transporters blended with PCBM result in efficient devices (Jsc up to 14 mA/cm2) due to rapid charge transfer and the

  2. Gate-induced superconductivity in a solution-processed organic polymer film

    NASA Astrophysics Data System (ADS)

    Schön, J. H.; Dodabalapur, A.; Bao, Z.; Kloc, Ch.; Schenker, O.; Batlogg, B.

    2001-03-01

    The electrical and optical properties of conjugated polymers have received considerable attention in the context of potentially low-cost replacements for conventional metals and inorganic semiconductors. Charge transport in these organic materials has been characterized in both the doped-metallic and the semiconducting state, but superconductivity has not hitherto been observed in these polymers. Here we report a distinct metal-insulator transition and metallic levels of conductivity in a polymer field-effect transistor. The active material is solution-cast regioregular poly(3-hexylthiophene), which forms relatively well ordered films owing to self-organization, and which yields a high charge carrier mobility (0.05-0.1cm2V-1s-1) at room temperature. At temperatures below ~2.35K with sheet carrier densities exceeding 2.5 × 1014cm-2, the polythiophene film becomes superconducting. The appearance of superconductivity seems to be closely related to the self-assembly properties of the polymer, as the introduction of additional disorder is found to suppress superconductivity. Our findings therefore demonstrate the feasibility of tuning the electrical properties of conjugated polymers over the largest range possible-from insulating to superconducting.

  3. Modification and characterization of fluorescent conjugated polymer nanoparticles for single molecule detection

    NASA Astrophysics Data System (ADS)

    Zheng, Yueli

    Single molecule tracking using fluorescent dye or nanoparticle labels has emerged as a useful technique for probing biomolecular processes. Considerable interest arises in the development of nanoparticle labels with brighter fluorescence in order to improve the spatial and temporal resolution of single molecule detection and to facilitate the application of single molecule detection methods to a wider range of intracellular processes. The McNeill laboratory recently reported that conjugated polymer nanoparticles exhibit fluorescence cross-sections roughly 10--100 times higher than other luminescent nanoparticles of similar size, excellent photostability (2.2x108 photons emitted per nanoparticle prior to photobleaching), and saturated emission rates roughly 100 times higher than that of the molecular dyes and more than 1000 times higher than that of colloidal semiconductor quantum dots. One purpose of this graduate research is the development of highly fluorescent, bioconjugated nanoparticle labels based on conjugated polymers for demanding fluorescence applications such as single molecule tracking in live cells. Three surface modification methods (conjugated polymer nanoparticles encapsulated with lipid silica agents, conjugated polymer nanoparticles encapsulated with tetraethyl orthosilicate(TEOS) and hybrid nanoparticles with thiol pendant groups by the Stober Method (3-mercaptopropyl trimethoxysilane (MPS))) have been developed to protect the conjugated polymer, passivate the nanoparticle surface, and provide a chemical handle for bioconjugation such as nanoparticle encapsulation with alkoxysilanes and Stober method. After encapsulation, the fluorescence quantum yield of silica-encapsulated nanoparticles is improved by 20% as compared to bare conjugated polymer nanoparticles, while the photostability is improved by a factor of 2, indicating that some protection of the polymer is provided by the encapsulating layer. Another purpose of my research is the

  4. Toward intrinsically stretchable organic semiconductors: mechanical properties of high-performance conjugated polymers

    NASA Astrophysics Data System (ADS)

    Sawyer, Eric J.; Savagatrup, Suchol; O'Connor, Timothy F.; Makaram, Aditya S.; Burke, Daniel J.; Zaretski, Aliaksandr V.; Printz, Adam D.; Lipomi, Darren J.

    2014-10-01

    This paper describes several approaches to understanding and improving the response of π-conjugated (semiconducting) polymers to tensile strain. Our principal goal was to establish the design criteria for introducing elasticity and ductility in conjugated (semiconducting) polymers through a rigorous analysis of the structural determinants of the mechanical properties of this type of material. We elucidated the details of the effect of the alkyl side chain length on the mechanical properties of regioregular polythiophene and used this analysis to select materials for stretching and transfer printing of organic solar cells to hemispherical substrates. This demonstration represents the first time that a conjugated polymer device has ever been stretched and conformally bonded to a complex 3D surface (i.e., other than a cone or cylinder, for which flexibility—as opposed to stretchability—is sufficient). We then further explored the details of the dependence of the mechanical properties on the side chain of a semiconducting polymer by synthesizing a series of hybrid materials (block and random copolymers) containing both short and long side chains. This analysis revealed the unusual semiconducting polymer, poly(3-heptylthiophene), as having an excellent combination of mechanical and electronic properties. In parallel, we explored a new method of producing "blocky" copolymers using a new procedure based on random segmentation of conjugated monomers. We found that introduction of structural randomness increased the elasticity without having detrimental effects on the photovoltaic performance. We also describe methods of synthesizing large volumes of conjugated polymers in environmentally benign ways that were amenable to manufacturing.

  5. Altering the Conjugation Pathway for Improved Performance of Benzobisoxazole-Based Polymer Guest Emitters in Polymer Light-Emitting Diodes

    SciTech Connect

    Intemann, Jeremy J.; Hellerich, Emily S.; Tlach, Brian C.; Ewan, Monique D.; Barnes, Charles A.; Bhuwalka, Achala; Cai, Min; Shinar, Joseph; Shinar, Ruth; Jeffries-EL, Malika

    2012-08-27

    Benzobisoxazoles (BBOs) are known to increase the electron affinities and improve the electron transporting properties of materials containing them. However, BBO copolymers generally do not perform well as emissive guests in guest–host PLEDs due to inefficient Förster resonance energy transfer (FRET) between host and guest. The incomplete FRET results in a large amount of host emission and limits the potential efficiencies of the devices. In all previously reported BBO copolymers, the conjugation pathway was through the oxazole rings. Herein we report six new BBO copolymers with backbone connectivity directly on the central benzene ring, resulting in a conjugation pathway for the polymers that is perpendicular to the previously reported pathway. Guest–host PLEDs made using these polymers show that the new conjugation pathway improves FRET between the poly(N-vinylcarbazole) host and the BBO-containing polymer guest. Because of highly efficient FRET, no host emission is observed even at lower guest concentrations. The improved energy transfer results in devices with luminous efficiencies up to 3.1 Cd/A, a 3-fold improvement over previously reported BBO-based PLEDs. These results indicate that the conjugation pathway plays a critical role in designing emissive materials for guest–host PLEDs.

  6. Polymer compositions, polymer films and methods and precursors for forming same

    SciTech Connect

    Klaehn, John R; Peterson, Eric S; Orme, Christopher J

    2013-09-24

    Stable, high performance polymer compositions including polybenzimidazole (PBI) and a melamine-formaldehyde polymer, such as methylated, poly(melamine-co-formaldehyde), for forming structures such as films, fibers and bulky structures. The polymer compositions may be formed by combining polybenzimidazole with the melamine-formaldehyde polymer to form a precursor. The polybenzimidazole may be reacted and/or intertwined with the melamine-formaldehyde polymer to form the polymer composition. For example, a stable, free-standing film having a thickness of, for example, between about 5 .mu.m and about 30 .mu.m may be formed from the polymer composition. Such films may be used as gas separation membranes and may be submerged into water for extended periods without crazing and cracking. The polymer composition may also be used as a coating on substrates, such as metal and ceramics, or may be used for spinning fibers. Precursors for forming such polymer compositions are also disclosed.

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

    PubMed Central

    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

  8. Super absorbent conjugated microporous polymers: a synergistic structural effect on the exceptional uptake of amines.

    PubMed

    Liu, Xiaoming; Xu, Yanhong; Guo, Zhaoqi; Nagai, Atsushi; Jiang, Donglin

    2013-04-21

    Conjugated microporous polymers exhibit a synergistic structural effect on the exceptional uptake of amines, whereas the dense porphyrin units facilitate uptake, the high porosity offers a large interface and the swellability boosts capacity. They are efficient in the uptake of both vapor and liquid amines, are applicable to various types of amines, and are excellent for cycle use.

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

    PubMed

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

    2016-03-02

    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.

  10. Thermoreversible Morphology and Conductivity of a Conjugated Polymer Network Embedded in Block Copolymer Self-Assemblies

    SciTech Connect

    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

    2016-07-19

    Self-assembly of block copolymers provides numerous opportunities to create functional materials, utilizing self-assembled microdomains with a variety of morphology and periodic architectures as templates for functional nanofillers. Here new progress is reported toward the fabrication of thermally responsive and electrically conductive polymeric self-assemblies made from a water-soluble poly(thiophene) derivative with short poly(ethylene oxide) side chains and Pluronic L62 block copolymer solution in water. The structural and electrical properties of conjugated polymer-embedded self-assembled architectures are investigated by combining small-angle neutron and X-ray scattering, coarse-grained molecular dynamics 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 micellarto- lamellar phase transition defines the embedded conjugated polymer network. As a result, 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. In conclusion, this study shows promise for enabling more flexibility in processing and utilizing water-soluble conjugated polymers in aqueous solutions for self-assembly based fabrication of stimuli-responsive nanostructures and sensory materials.

  11. Thermoreversible Morphology and Conductivity of a Conjugated Polymer Network Embedded in Block Copolymer Self-Assemblies

    DOE PAGES

    Han, Youngkyu; Carrillo, Jan-Michael Y.; Zhang, Zhe; ...

    2016-07-19

    Self-assembly of block copolymers provides numerous opportunities to create functional materials, utilizing self-assembled microdomains with a variety of morphology and periodic architectures as templates for functional nanofillers. Here new progress is reported toward the fabrication of thermally responsive and electrically conductive polymeric self-assemblies made from a water-soluble poly(thiophene) derivative with short poly(ethylene oxide) side chains and Pluronic L62 block copolymer solution in water. The structural and electrical properties of conjugated polymer-embedded self-assembled architectures are investigated by combining small-angle neutron and X-ray scattering, coarse-grained molecular dynamics simulations, and impedance spectroscopy. The L62 solution template organizes the conjugated polymers by stably incorporatingmore » them into the hydrophilic domains thus inhibiting aggregation. The changing morphology of L62 during the micellarto- lamellar phase transition defines the embedded conjugated polymer network. As a result, 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. In conclusion, this study shows promise for enabling more flexibility in processing and utilizing water-soluble conjugated polymers in aqueous solutions for self-assembly based fabrication of stimuli-responsive nanostructures and sensory materials.« less

  12. Development and Characterization of New Donor-Acceptor Conjugated Polymers and Fullerene Nanoparticles for High Performance Bulk Heterojunction Solar Cells

    DTIC Science & Technology

    2011-01-14

    Nanoparticles for High Performance Bulk Heterojunction Solar Cells Jan. 14,2011 Name of Principal Investigators: Kung-Hwa Wei - e-mail address : khwei...donor-π-bridge-acceptor side chains for high efficiency polymer solar cells . Different from the commonly used linear D-A conjugated polymers, the...Development and Characterization of New Donor-Acceptor Conjugated Polymers and Fullerene Nanoparticles for High Performance Bulk Heterojunction Solar Cells

  13. Hot pen and laser writable photonic polymer films

    NASA Astrophysics Data System (ADS)

    Moirangthem, Monali; Stumpel, Jelle E.; Alp, Baran; Teunissen, Pit; Bastiaansen, Cees W. M.; Schenning, Albertus P. H. J.

    2016-03-01

    An orange-reflecting photonic polymer film has been fabricated based on a hydrogen-bonded cholesteric liquid crystalline (CLC) polymer consisting of non-reactive (R)-(+)-3-methyladipic acid as the chiral dopant. This polymer film can be patterned easily by evaporating the chiral dopant at specific locations with a hot pen or a laser beam. Removal of chiral dopant leads to a decrease in the helical pitch at the heat treated areas leading to a change in color from orange to green revealing a high contrast pattern. The photonic patterns are irreversible and stable at ambient conditions. This makes such a CLC polymer film interesting as writable photonic paper.

  14. Solution-processed small molecule-polymer blend organic thin-film transistors with hole mobility greater than 5 cm2/Vs.

    PubMed

    Smith, Jeremy; Zhang, Weimin; Sougrat, Rachid; Zhao, Kui; Li, Ruipeng; Cha, Dongkyu; Amassian, Aram; Heeney, Martin; McCulloch, Iain; Anthopoulos, Thomas D

    2012-05-08

    Using phase-separated organic semiconducting blends containing a small molecule, as the hole transporting material, and a conjugated amorphous polymer, as the binder material, we demonstrate solution-processed organic thin-film transistors with superior performance characteristics that include; hole mobility >5 cm(2) /Vs, current on/off ratio ≥10(6) and narrow transistor parameter spread. These exceptional characteristics are attributed to the electronic properties of the binder polymer and the advantageous nanomorphology of the blend film.

  15. π-Conjugated Organometallic Isoindigo Oligomer and Polymer Chromophores: Singlet and Triplet Excited State Dynamics and Application in Polymer Solar Cells.

    PubMed

    Goswami, Subhadip; Gish, Melissa K; Wang, Jiliang; Winkel, Russell W; Papanikolas, John M; Schanze, Kirk S

    2015-12-09

    An isoindigo based π-conjugated oligomer and polymer that contain cyclometalated platinum(II) "auxochrome" units were subjected to photophysical characterization, and application of the polymer in bulk heterojunction polymer solar cells with PCBM acceptor was examined. The objective of the study was to explore the effect of the heavy metal centers on the excited state properties, in particular, intersystem crossing to a triplet (exciton) state, and further how this would influence the performance of the organometallic polymer in solar cells. The materials were characterized by electrochemistry, ground state absorption, emission, and picosecond-nanosecond transient absorption spectroscopy. Electrochemical measurements indicate that the cyclometalated units have a significant impact on the HOMO energy level of the chromophores, but little effect on the LUMO, which is consistent with localization of the LUMO on the isoindigo acceptor unit. Picosecond-nanosecond transient absorption spectroscopy reveals a transient with ∼100 ns lifetime that is assigned to a triplet excited state that is produced by intersystem crossing from a singlet state on a time scale of ∼130 ps. This is the first time that a triplet state has been observed for isoindigo π-conjugated chromophores. The performance of the polymer in bulk heterojunction solar cells was explored with PC61BM as an acceptor. The performance of the cells was optimum at a relatively high PCBM loading (1:6, polymer:PCBM), but the overall efficiency was relatively low with power conversion efficiency (PCE) of 0.22%. Atomic force microscopy of blend films reveals that the length scale of the phase separation decreases with increasing PCBM content, suggesting a reason for the increase in PCE with acceptor loading. Energetic considerations show that the triplet state in the polymer is too low in energy to undergo charge separation with PCBM. Further, due to the relatively low LUMO energy of the polymer, charge transfer

  16. Kinetic Effects on Self-Assembly and Function of Protein-Polymer Bioconjugates in Thin Films Prepared by Flow Coating.

    PubMed

    Chang, Dongsook; Huang, Aaron; Olsen, Bradley D

    2017-01-01

    The self-assembly of nanostructured globular protein arrays in thin films is demonstrated using protein-polymer block copolymers based on a model protein mCherry and the polymer poly(oligoethylene glycol acrylate) (POEGA). Conjugates are flow coated into thin films on a poly(ethylene oxide) grafted Si surface, forming self-assembled cylindrical nanostructures with POEGA domains selectively segregating to the air-film interface. Long-range order and preferential arrangement of parallel cylinders templated by selective surfaces are demonstrated by controlling relative humidity. Long-range order increases with coating speed when the film thicknesses are kept constant, due to reduced nucleation per unit area of drying film. Fluorescence emission spectra of mCherry in films prepared at <25% relative humidity shows a small shift suggesting that proteins are more perturbed at low humidity than high humidity or the solution state.

  17. Kinetic Effects on Self-Assembly and Function of Protein-Polymer Bioconjugates in Thin Films Prepared by Flow Coating

    SciTech Connect

    Chang, Dongsook; Huang, Aaron; Olsen, Bradley D.

    2016-11-04

    The self-assembly of nanostructured globular protein arrays in thin films is demonstrated using protein–polymer block copolymers based on a model protein mCherry and the polymer poly(oligoethylene glycol acrylate) (POEGA). Conjugates are flow coated into thin films on a poly(ethylene oxide) grafted Si surface, forming self-assembled cylindrical nanostructures with POEGA domains selectively segregating to the air–film interface. Long-range order and preferential arrangement of parallel cylinders templated by selective surfaces are demonstrated by controlling relative humidity. Long-range order increases with coating speed when the film thicknesses are kept constant, due to reduced nucleation per unit area of drying film. Fluorescence emission spectra of mCherry in films prepared at <25% relative humidity shows a small shift suggesting that proteins are more perturbed at low humidity than high humidity or the solution state.

  18. Enhancing charge storage of conjugated polymer electrodes with phenolic acids

    NASA Astrophysics Data System (ADS)

    Wagner, Michal; Rębiś, Tomasz; Inganäs, Olle

    2016-01-01

    We here present studies of electrochemical doping of poly(1-aminoanthraquinone) (PAAQ) films with three structurally different phenolic acids. The examined phenolic acids (sinapic, ferulic and syringic acid) were selected due to their resemblance to redox active groups, which can be found in lignin. The outstanding electrochemical stability of PAAQ films synthesized for this work enabled extensive cycling of phenolic acid-doped PAAQ films. Potentiodynamic and charge-discharge studies revealed that phenolic acid-doped PAAQ films exhibited enhanced capacitance in comparison to undoped PAAQ films, together with appearance of redox activity characteristics specific for each dopant. Electrochemical kinetic studies performed on microelectrodes affirmed the fast electron transfer for hydroquinone-to-quinone reactions with these phenolic compounds. These results imply the potential application of phenolic acids in cheap and degradable energy storage devices.

  19. The thin-film deposition of conjugated molecules for organic electronics

    NASA Astrophysics Data System (ADS)

    Jin, Michael H.-C.

    2008-06-01

    Device-quality conjugated organic thin films are now routinely prepared in many different ways to fabricate light-emitting diodes, thin-film transistors, and photovoltaic devices. Understanding how to design molecules through versatile synthetic chemistry and the mechanisms of phase transformation and chemical reaction that occur during the thin-film deposition process becomes especially vital for the performance of the applications. This article reviews the current understanding of various thin-film deposition technologies for the conjugated organic molecules primarily used in optoelectronics, particularly in photovoltaic applications.

  20. Mechanistic studies of the structure-photostability relationship of organic conjugated polymers

    NASA Astrophysics Data System (ADS)

    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. Polymer-drug conjugates for intracellar molecule-targeted photoinduced inactivation of protein and growth inhibition of cancer cells

    NASA Astrophysics Data System (ADS)

    Wang, Bing; Yuan, Huanxiang; Zhu, Chunlei; Yang, Qiong; Lv, Fengting; Liu, Libing; Wang, Shu

    2012-10-01

    For most molecule-targeted anticancer systems, intracellular protein targets are very difficult to be accessed by antibodies, and also most efforts are made to inhibit protein activity temporarily rather than inactivate them permanently. In this work we firstly designed and synthesized multifunctional polymer-drug conjugates (polythiophene-tamoxifen) for intracellular molecule-targeted binding and inactivation of protein (estrogen receptor α, ERα) for growth inhibition of MCF-7 cancer cells. Small molecule drug was conjugated to polymer side chain for intracellular signal protein targeting, and simultaneously the fluorescent characteristic of polymer for tracing the cellular uptake and localization of polythiophene-drug conjugates by cell imaging. Under light irradiation, the conjugated polymer can sensitize oxygen to produce reactive oxygen species (ROS) that specifically inactivate the targeted protein, and thus inhibit the growth of tumor cells. The conjugates showed selective growth inhibition of ERα positive cancer cells, which exhibits low side effect for our intracellular molecule-targeted therapy system.

  2. Synthesis of carboxylated poly(NIPAAm) oligomers and their application to form thermo-reversible polymer-enzyme conjugates.

    PubMed

    Chen, G; Hoffman, A S

    1994-01-01

    A thermo-reversible poly(N-isopropylacrylamide) poly(NIPAAm) oligomer with a carboxyl functional end group has been synthesized by radical polymerization using beta-mercaptopropionic acid as a chain transfer reagent. This polymer has been conjugated to an enzyme, beta-D-glucosidase, to form a thermo-reversible water soluble-insoluble polymer-enzyme conjugate. This conjugate can be used for separation, recovery and recycle of an enzyme simply by applying small temperature changes to the reaction medium. In contrast to the random polymer-enzyme conjugates reported in the literature, in this study the enzyme is coupled to each polymer chain by a single end attachment. These preliminary studies show that the conjugated enzyme exhibits very high retention of activity (> 90%) compared to the native enzyme and shows improved thermal stability.

  3. Thermogelling polymer-platinum(IV) conjugates for long-term delivery of cisplatin.

    PubMed

    Shen, Wenjia; Luan, Jiabin; Cao, Luping; Sun, Jian; Yu, Lin; Ding, Jiandong

    2015-01-12

    In this study, we suggest a novel strategy of constituting an in situ-formed hydrogel composed of polymer-platinum(IV) conjugate to realize a long-term delivery of cisplatin. A unique conjugate was designed and synthesized by covalent linking of Pt(IV) complex to the hydrophobic end of two methoxyl poly(ethylene glycol)-b-poly(d,l-lactide) (mPEG-PLA) copolymer chains, resulting in the formation of Bi(mPEG-PLA)-Pt(IV). The conjugate could self-assemble into micelles in water, and its concentrated solution exhibited a thermoreversible sol-gel transition and formed a semisolid thermogel at body temperature. The incorporation of the cisplatin analogue Pt(IV) prodrug into the conjugate had a significant influence on its thermogelling properties and the conjugate thermogelation was attributed to the micellar aggregation. In vitro release experiments of Pt(IV)-conjugated thermogel showed that the platinum release lasted as long as two months. Furthermore, we demonstrated that the Pt(IV) prodrug was released mainly in the form of micelles and micellar aggregates from the gel depot. Compared with free cisplatin, the formation of conjugate micelles led to the enhanced in vitro cytotoxicity against cancer cells due to the effective accumulation into cells via endocytosis.

  4. Electrospun conjugated polymer nanofibers as miniaturized light sources: control of morphology, optical properties, and assembly

    NASA Astrophysics Data System (ADS)

    Camposeo, A.; Fasano, V.; Moffa, M.; Polini, A.; Di Camillo, D.; Ruggieri, F.; Santucci, S.; Lozzi, L.; Persano, L.; Pisignano, D.

    2014-10-01

    Light-emitting nanostructures made by conjugated polymers show interesting emission and electronic properties. In this work we report on novel approaches for the fabrication and control of light-emitting nanofibers by electrospinning. The shape, size and light-emitting properties of the fibers can be specifically tailored by acting on the composition of the solution used for the electrospinning process, an approach allowing for obtaining fibers ranging from micrometer-sized ribbons to almost cylindrical fibers with diameters down to few hundreds of nanometers. Moreover, following proper process optimization these fibers can also be precisely positioned in ordered arrays by near-field electrospinning, a method that exploits the stable region of the polymer jet. The possibility of precisely shaping the conjugated polymer fibers and of assembling the fiber in ordered arrays, combined with enhanced emission properties, opens interesting perspectives for developing novel emitting flexible nanomaterials suitable for light sourcing and optical sensing.

  5. Intracellular delivery and trafficking dynamics of a lymphoma-targeting antibody-polymer conjugate.

    PubMed

    Berguig, Geoffrey Y; Convertine, Anthony J; Shi, Julie; Palanca-Wessels, Maria Corinna; Duvall, Craig L; Pun, Suzie H; Press, Oliver W; Stayton, Patrick S

    2012-12-03

    Ratiometric fluorescence and cellular fractionation studies were employed to characterize the intracellular trafficking dynamics of antibody-poly(propylacrylic acid) (PPAA) conjugates in CD22+ RAMOS-AW cells. The HD39 monoclonal antibody (mAb) directs CD22-dependent, receptor-mediated uptake in human B-cell lymphoma cells, where it is rapidly trafficked to the lysosomal compartment. To characterize the intracellular-release dynamics of the polymer-mAb conjugates, HD39-streptavidin (HD39/SA) was dual-labeled with pH-insensitive Alexa Fluor 488 and pH-sensitive pHrodo fluorophores. The subcellular pH distribution of the HD39/SA-polymer conjugates was quantified as a function of time by live-cell fluorescence microscopy, and the average intracellular pH value experienced by the conjugates was also characterized as a function of time by flow cytometry. PPAA was shown to alter the intracellular trafficking kinetics strongly relative to HD39/SA alone or HD39/SA conjugates with a control polymer, poly(methacryclic acid) (PMAA). Subcellular trafficking studies revealed that after 6 h, only 11% of the HD39/SA-PPAA conjugates had been trafficked to acidic lysosomal compartments with values at or below pH 5.6. In contrast, the average intracellular pH of HD39/SA alone dropped from 6.7 ± 0.2 at 1 h to 5.6 ± 0.5 after 3 h and 4.7 ± 0.6 after 6 h. Conjugation of the control polymer PMAA to HD39/SA showed an average pH drop similar to that of HD39/SA. Subcellular fractionation studies with tritium-labeled HD39/SA demonstrated that after 6 h, 89% of HD39/SA was associated with endosomes (Rab5+) and lysosomes (Lamp2+), while 45% of HD39/SA-PPAA was translocated to the cytosol (lactate dehydrogenase+). These results demonstrate the endosomal-releasing properties of PPAA with antibody-polymer conjugates and detail their intracellular trafficking dynamics and subcellular compartmental distributions over time.

  6. Low bandgap conjugated polymers for organic solar cells

    NASA Astrophysics Data System (ADS)

    Xu, Tao

    Organic solar cells are emerging as a potential solution to address the energy issue in the future. Functional materials that can achieve high performance are the main topics in my thesis. I went briefly to introduce the background and history first, emphasizing on the synthetic principles towards high performance copolymers. My second chapters is about the perturbation effect by introducing terminal chloroaryl in the side chain. A new type of monomer is presented in Chapter III and corresponding polymers are studied. Then we investigated the impact of polymerization conditions on the physical properties using PTB7 as the standard polymer. In the last, we further utilized TID unit to construct acceptor polymers and random copolymer. A PCE value of 7.55% was achieved.

  7. 11.4% Efficiency non-fullerene polymer solar cells with trialkylsilyl substituted 2D-conjugated polymer as donor

    PubMed Central

    Bin, Haijun; Gao, Liang; Zhang, Zhi-Guo; Yang, Yankang; Zhang, Yindong; Zhang, Chunfeng; Chen, Shanshan; Xue, Lingwei; Yang, Changduk; Xiao, Min; Li, Yongfang

    2016-01-01

    Simutaneously high open circuit voltage and high short circuit current density is a big challenge for achieving high efficiency polymer solar cells due to the excitonic nature of organic semdonductors. Herein, we developed a trialkylsilyl substituted 2D-conjugated polymer with the highest occupied molecular orbital level down-shifted by Si–C bond interaction. The polymer solar cells obtained by pairing this polymer with a non-fullerene acceptor demonstrated a high power conversion efficiency of 11.41% with both high open circuit voltage of 0.94 V and high short circuit current density of 17.32 mA cm−2 benefitted from the complementary absorption of the donor and acceptor, and the high hole transfer efficiency from acceptor to donor although the highest occupied molecular orbital level difference between the donor and acceptor is only 0.11 eV. The results indicate that the alkylsilyl substitution is an effective way in designing high performance conjugated polymer photovoltaic materials. PMID:27905397

  8. 11.4% Efficiency non-fullerene polymer solar cells with trialkylsilyl substituted 2D-conjugated polymer as donor

    NASA Astrophysics Data System (ADS)

    Bin, Haijun; Gao, Liang; Zhang, Zhi-Guo; Yang, Yankang; Zhang, Yindong; Zhang, Chunfeng; Chen, Shanshan; Xue, Lingwei; Yang, Changduk; Xiao, Min; Li, Yongfang

    2016-12-01

    Simutaneously high open circuit voltage and high short circuit current density is a big challenge for achieving high efficiency polymer solar cells due to the excitonic nature of organic semdonductors. Herein, we developed a trialkylsilyl substituted 2D-conjugated polymer with the highest occupied molecular orbital level down-shifted by Si-C bond interaction. The polymer solar cells obtained by pairing this polymer with a non-fullerene acceptor demonstrated a high power conversion efficiency of 11.41% with both high open circuit voltage of 0.94 V and high short circuit current density of 17.32 mA cm-2 benefitted from the complementary absorption of the donor and acceptor, and the high hole transfer efficiency from acceptor to donor although the highest occupied molecular orbital level difference between the donor and acceptor is only 0.11 eV. The results indicate that the alkylsilyl substitution is an effective way in designing high performance conjugated polymer photovoltaic materials.

  9. 11.4% Efficiency non-fullerene polymer solar cells with trialkylsilyl substituted 2D-conjugated polymer as donor.

    PubMed

    Bin, Haijun; Gao, Liang; Zhang, Zhi-Guo; Yang, Yankang; Zhang, Yindong; Zhang, Chunfeng; Chen, Shanshan; Xue, Lingwei; Yang, Changduk; Xiao, Min; Li, Yongfang

    2016-12-01

    Simutaneously high open circuit voltage and high short circuit current density is a big challenge for achieving high efficiency polymer solar cells due to the excitonic nature of organic semdonductors. Herein, we developed a trialkylsilyl substituted 2D-conjugated polymer with the highest occupied molecular orbital level down-shifted by Si-C bond interaction. The polymer solar cells obtained by pairing this polymer with a non-fullerene acceptor demonstrated a high power conversion efficiency of 11.41% with both high open circuit voltage of 0.94 V and high short circuit current density of 17.32 mA cm(-2) benefitted from the complementary absorption of the donor and acceptor, and the high hole transfer efficiency from acceptor to donor although the highest occupied molecular orbital level difference between the donor and acceptor is only 0.11 eV. The results indicate that the alkylsilyl substitution is an effective way in designing high performance conjugated polymer photovoltaic materials.

  10. Structure in Thin and Ultrathin Spin-Cast Polymer Films

    NASA Astrophysics Data System (ADS)

    Frank, C. W.; Rao, V.; Despotopoulou, M. M.; Pease, R. F. W.; Hinsberg, W. D.; Miller, R. D.; Rabolt, J. F.

    1996-08-01

    The molecular organization in ultrathin polymer films (thicknesses less than 1000 angstroms) and thin polymer films (thicknesses between 1000 and 10,000 angstroms) may differ substantially from that of bulk polymers, which can lead to important differences in resulting thermophysical properties. Such constrained geometry films have been fabricated from amorphous poly(3-methyl-4-hydroxy styrene) (PMHS) and semicrystalline poly(di-n-hexyl silane) (PD6S) by means of spin-casting. The residual solvent content is substantially greater in ultrathin PMHS films, which suggests a higher glass transition temperature that results from a stronger hydrogen-bonded network as compared with that in thicker films. Crystallization of PD6S is substantially hindered in ultrathin films, in which a critical thickness of 150 angstroms is needed for crystalline morphology to exist and in which the rate of crystallization is initially slow but increases rapidly as the film approaches 500 angstroms in thickness.

  11. A heparin-mimicking polymer conjugate stabilizes basic fibroblast growth factor

    NASA Astrophysics Data System (ADS)

    Nguyen, Thi H.; Kim, Sung-Hye; Decker, Caitlin G.; Wong, Darice Y.; Loo, Joseph A.; Maynard, Heather D.

    2013-03-01

    Basic fibroblast growth factor (bFGF) is a protein that plays a crucial role in diverse cellular functions, from wound healing to bone regeneration. However, a major obstacle to the widespread application of bFGF is its inherent instability during storage and delivery. Here, we describe the stabilization of bFGF by covalent conjugation with a heparin-mimicking polymer, a copolymer consisting of styrene sulfonate units and methyl methacrylate units bearing poly(ethylene glycol) side chains. The bFGF conjugate of this polymer retained bioactivity after synthesis and was stable to a variety of environmentally and therapeutically relevant stressors—such as heat, mild and harsh acidic conditions, storage and proteolytic degradation—unlike native bFGF. Following the application of stress, the conjugate was also significantly more active than the control conjugate system in which the styrene sulfonate units were omitted from the polymer structure. This research has important implications for the clinical use of bFGF and for the stabilization of heparin-binding growth factors in general.

  12. Anisotropic Conjugated Polymer Chain Conformation Tailors the Energy Migration in Nanofibers

    PubMed Central

    2016-01-01

    Conjugated polymers are complex multichromophore systems, with emission properties strongly dependent on the electronic energy transfer through active subunits. 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 time scale of picoseconds. These aligned and more extended chromophores, resulting from the high stretching rate and electric field applied during the fiber spinning process, lead to improved emission properties. Conjugated polymer fibers are relevant to develop optoelectronic plastic devices with enhanced and anisotropic properties. PMID:27933935

  13. Anisotropic Conjugated Polymer Chain Conformation Tailors the Energy Migration in Nanofibers.

    PubMed

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

    2016-11-30

    Conjugated polymers are complex multichromophore systems, with emission properties strongly dependent on the electronic energy transfer through active subunits. 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 time scale of picoseconds. These aligned and more extended chromophores, resulting from the high stretching rate and electric field applied during the fiber spinning process, lead to improved emission properties. Conjugated polymer fibers are relevant to develop optoelectronic plastic devices with enhanced and anisotropic properties.

  14. Preparation of redox polymer cathodes for thin film rechargeable batteries

    DOEpatents

    Skotheim, Terje A.; Lee, Hung S.; Okamoto, Yoshiyuki

    1994-11-08

    The present invention relates to the manufacture of thin film solid state electrochemical devices using composite cathodes comprising a redox polymer capable of undergoing oxidation and reduction, a polymer solid electrolyte and conducting carbon. The polymeric cathode material is formed as a composite of radiation crosslinked polymer electrolytes and radiation crosslinked redox polymers based on polysiloxane backbones with attached organosulfur side groups capable of forming sulfur-sulfur bonds during electrochemical oxidation.

  15. Modified extended Hückel band calculations on conjugated polymers

    NASA Astrophysics Data System (ADS)

    Hong, Sung Y.; Marynick, Dennis S.

    1992-04-01

    In order to more accurately predict band gaps, corresponding to π-π* transitions of one-dimensional conducting polymers, the formula for the off-diagonal elements, Hαβij in the extended Hückel (EH) band calculation method was modified according to the form Hαβij=K1(Hααii +Hββjj)exp(-K2Rαβ) Sαβij. Parametrizations for the constants K1 and K2 were performed so as to yield reasonable band gaps for the pure hydrocarbon polymers trans-polyacetylene, poly(para-phenylene), and poly(phenylene vinylene). Since there is a large difference in bond alternations along polymeric chains between ab initio and modified neglect of diatomic overlap optimized geometries, especially for heterocyclic polymers, the valence orbital exponents of oxygen, nitrogen, and sulfur were separately adjusted, depending on the chosen geometry, to reproduce the band gaps of polyfuran, polypyrrole, and polythiophene. It is found that geometrical relaxations in the presence of heteroatoms strongly affect the C1-C4 interactions as well as bond alternations, which in turn affect the band gap. Modified EH band calculations were performed for various polymers. The predicted band gaps had average errors of ca. 10% (less than 0.3 eV) compared to the experimental values, and the method produced band structures consistent with electron-energy-loss spectroscopic observations.

  16. Ferritin-Polymer Conjugates: Grafting Chemistry and Self-Assembly

    DTIC Science & Technology

    2009-10-26

    polymer core-shell structures by co-assembly. 9 A numbers of BNPs including cowpea mosaic virus, turnip yellow mosaic virus, and bacteriophage P22...Figure 11. Synthetic route for fluorescent crosslinkers. Turnip yellow mosaic virus (TYMV), a plant virus with unique structural and chemical

  17. Research on the electronic and optical properties of polymer and other organic molecular thin films

    SciTech Connect

    1997-02-01

    The main goal of the work is to find materials and methods of optimization of organic layered electroluminescent cells and to study such properties of polymers and other organic materials that can be used in various opto-electronic devices. The summary of results obtained during the first year of work is presented. They are: (1) the possibility to produce electroluminescent cells using a vacuum deposition photoresist technology for commercial photoresists has been demonstrated; (2) the idea to replace the polyaryl polymers by other polymers with weaker hole conductivity for optimization of electroluminescent cells with ITO-Al electrodes has been suggested. The goal is to obtain amorphous processable thin films of radiative recombination layers in electroluminescent devices; (3) procedures of preparation of high-quality vacuum-deposited poly (p-phenylene) (PPP) films on various substrates have been developed; (4) it was found for the first time that the fluorescence intensity of PPP films depends on the degree of polymerization; (5) the role of interfaces between organic compounds, on one side, and metals or semiconductors, on the other side, has been studied and quenching of the fluorescence caused by semiconductor layer in thin sandwiches has been observed; (6) studies of the dynamics of photoexcitations revealed the exciton self-trapping in quasi-one-dimensional aggregates; and (7) conditions for preparation of highly crystalline fullerene C{sub 60} films by vacuum deposition have been found. Composites of C{sub 60} with conjugated polymers have been prepared.

  18. Preparation of thin polymer films for infrared reaction rate studies

    NASA Technical Reports Server (NTRS)

    Garrard, G. G.; Houston, D. W.

    1970-01-01

    Procedure for preparing thin films for infrared spectrophotometric analysis involves pressing of a neat mixture of reactants between nonreactive thin polymer films with noninterfering absorption bands. Pressing is done under a pressure that gives desirable thickness. Following this process, the film sandwich is cut to accommodate the laboratory instrument.

  19. Preparation of Conjugated Polymer Grafted with H2O2-Sensitive Prodrug for Cell Imaging and Tumor Cell Killing.

    PubMed

    Li, Meng; Li, Shengliang; Chen, Hui; Hu, Rong; Liu, Libing; Lv, Fengting; Wang, Shu

    2016-01-13

    In this work, a new conjugated polymer poly(fluorene-co-phenylene) derivative containing pendent quaternized chlormethine (PFP-Chl) was synthesized by covalent linking small molecular prodrug groups onto conjugated polymer side chains. H2O2-sensitive prodrug with an eight-member-cyclic boronate ester structure could suffer from H2O2-triggered nitrogen mustard release and further DNA cross-linking and alkylation. PFP-Chl combines therapeutic characteristic with excellent optical property of conjugated polymers. It is found that PFP-Chl could enter into cells by endocytosis to simultaneously exhibit abilities of fluorescent imaging and tumor cell inhibition.

  20. Thermochemical study of amino acid imprinted polymer films.

    PubMed

    Chai, Ziyi; BelBruno, Joseph J

    2015-11-01

    Molecularly imprinted polymers provide an alternative to traditional methods of amino acid analysis. The imprinted polymers are more robust and significantly less expensive than, for example, ELISA analysis. Amino acid imprinted nylon-6 thin films were studied by differential scanning calorimetry and scanning electron microscopy. Endothermic peaks were observed for imprinted films at temperatures higher than that for pure nylon, indicating the formation of a more-ordered, hydrogen bonded polymer. Removal of the amino acid from the imprinted film resulted in reversion to the peak observed for pure nylon-6. Additives, β-cyclodextrin and multiwalled carbon nanotubes, were added to the imprinted polymer solutions as a means to increase the porosity of the films. These studies resulted in alternative morphologies and calorimetric results that provide additional functionalities and applications for imprinted polymers.

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

    NASA Astrophysics Data System (ADS)

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

    2011-03-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2016-12-01

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

  3. Multivalent Polymers for Drug Delivery and Imaging: The Challenges of Conjugation

    PubMed Central

    2015-01-01

    Multivalent polymers offer a powerful opportunity to develop theranostic materials on the size scale of proteins that can provide targeting, imaging, and therapeutic functionality. Achieving this goal requires the presence of multiple targeting molecules, dyes, and/or drugs on the polymer scaffold. This critical review examines the synthetic, analytical, and functional challenges associated with the heterogeneity introduced by conjugation reactions as well as polymer scaffold design. First, approaches to making multivalent polymer conjugations are discussed followed by an analysis of materials that have shown particular promise biologically. Challenges in characterizing the mixed ligand distributions and the impact of these distributions on biological applications are then discussed. Where possible, molecular-level interpretations are provided for the structures that give rise to the functional ligand and molecular weight distributions present in the polymer scaffolds. Lastly, recent strategies employed for overcoming or minimizing the presence of ligand distributions are discussed. This review focuses on multivalent polymer scaffolds where average stoichiometry and/or the distribution of products have been characterized by at least one experimental technique. Key illustrative examples are provided for scaffolds that have been carried forward to in vitro and in vivo testing with significant biological results. PMID:25120091

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

    PubMed Central

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

    2016-01-01

    σ-π conjugated polymer strategy is proposed for designing electroluminescent host polymers with silylene-diphenylene as the backbone repeat unit giving a high triplet energy (ET = 2.67 eV). By incorporation of high ET (3.0 eV) electron (oxadiazole, OXD) and hole (triphenyl amine, TPA) transport moieties, or TPA alone (in this case, the main chain acts as electron transport channel) as side arms on the silylene, the high ET bipolar and unipolar polymers are formed, allowing a use of iridium green phosphor (Ir(ppy)2(acac), Ir-G) (ET = 2.40 eV) as the dopant. The matching of energy levels of the dopant with the hosts, leading to charge trapping into it; and singlets and triplets of the exciplex and excimer can be harvested via energy transfer to the dopant. Using these host-guest systems as the emitting layer, chlorinated indium-tin-oxide (Cl-ITO) as the anode, and benzimidazole derivative (TPBI) as the electron transport layer, this two-layer device gives the high luminance efficiency 80.1 cd/A and external quantum efficiency 21.2%, which is the best among the report values for polymer light emitting diode (PLED) in the literatures. This example manifests that σ-π conjugated polymer strategy is a promising route for designing polymer host for efficient electrophosphorescence. PMID:27910921

  5. Effectiveness of External Electric Field Treatment of Conjugated Polymers in Bulk-Heterojunction Solar Cells.

    PubMed

    Solanki, Ankur; Bagui, Anirban; Long, Guankui; Wu, Bo; Salim, Teddy; Chen, Yongsheng; Lam, Yeng Ming; Sum, Tze Chien

    2016-11-30

    External electric field treatment (EFT) on P3HT:PCBM bulk heterojunction (BHJ) devices was recently found to be a viable approach for improving the power conversion efficiencies (PCEs) through modulating the blend nanomorphology. However, its effectiveness over the broad family of polymer-fullerene blends remains unclear. Herein, we investigate the effects of external EFT on various polymer-fullerene blends with distinct morphologies stemming from the difference in molecular structure of the polymers (i.e., semicrystalline vs amorphous) in a bid to establish a clear morphology-function-charge dynamics relationship to the photovoltaic performance. Our findings reveal that EFT promotes self-organization of the semicrystalline thiophene-based conjugated polymers (i.e., P3HT and P3BT) while it was ineffective for the amorphous polymers (i.e., PTB7 and PCPDTBT) even at the maximum applied E-field of 8 kV cm(-1). Transient absorption spectroscopy shows an improvement in the initial charge-carrier and polaron formation from delocalized excitons in the E-field treated semicrystalline blends compared to their untreated reference samples. Interfacial trap-assisted monomolecular and trap-free bimolecular recombination at nanosecond-microsecond time scale in the E-field treated P3BT:PC60BM devices are significantly suppressed. Importantly, our findings shed new light and provide guidelines on the effectiveness of utilizing external EFT to enhance the PCEs of a larger family of conjugated polymer-based BHJ OSCs.

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

    PubMed Central

    Tan, Gamze; Kantner, Karsten; Zhang, Qian; Soliman, Mahmoud G.; del Pino, Pablo; Parak, Wolfgang J.; Onur, Mehmet A.; Valdeperez, Daniel; Rejman, Joanna; Pelaz, Beatriz

    2015-01-01

    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. PMID:28347065

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

    NASA Astrophysics Data System (ADS)

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

    2016-09-01

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

  8. Poled polymer films for nonlinear optics

    SciTech Connect

    Singer, K.D.; Kuzyk, M.G.; Holland, W.R.; Cahill, P.A.

    1989-01-01

    Second harmonic generation was measured for a thin corona-poled film of a dicyanovinyl azo dye incorporated in the side-chain methacrylate polymer. Measurements were performed at a wavelength of 1.58 ..mu..m as a function of incident angle for both p- and s-polarized incident light. From these measurements the form and magnitude of the second harmonic coefficient tensor were determined. The molecular distribution implied by the data is consistent with a thermodynamic potential containing only the dipolar orienting energy acting during poling. We have also demonstrated anomalous-dispersion phase-matched second harmonic generation for the first time using electric field induced second harmonic generation (EFISH) in a liquid solution of Foron Brilliant Blue S-R (FBB). Results are described. 10 refs., 4 figs., 2 tabs.

  9. Enzyme immobilization on reactive polymer films.

    PubMed

    Cordeiro, Ana L; Pompe, Tilo; Salchert, Katrin; Werner, Carsten

    2011-01-01

    Immobilized enzymes are currently used in many bioanalytical and biomedical applications. This protocol describes the use of thin films of maleic anhydride copolymers to covalently attach enzymes directly to solid supports at defined concentrations. The concentration and activity of the surface-bound enzymes can be tuned over a wide range by adjusting the concentration of enzyme used for immobilization and the physicochemical properties of the polymer platform, as demonstrated here for the proteolytic enzyme Subtilisin A. The versatile method presented allows for the immobilization of biomolecules containing primary amino groups to a broad variety of solid carriers, ranging from silicon oxide surfaces to standard polystyrene well plates and metallic surfaces. The approach can be used to investigate the effects of immobilized enzymes on cell adhesion, and on the catalysis of specific reactions.

  10. Novel enzyme-polymer conjugates for biotechnological applications

    PubMed Central

    Romero, Oscar; Rivero, Cintia W.; Guisan, Jose M.

    2013-01-01

    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%. PMID:23638362

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

    DTIC Science & Technology

    2012-09-20

    applications and other devices of interest to the Air Force with a special focus on photodetectors (especially in the near infrared), solar cells , and...to be used as the active polymer in PCBM based solar cells . 6 Simplifying our chemistry, we have developed Stille coupling polymerization...weight illustrated in Table 1, such as the Mn = 30.5 kDa (red) and 35.1 kDa (blue) prepared via the Stille method provided effective solar cell

  12. Measurements of Photo-induced Changes in Conjugated Polymers

    DOE R&D Accomplishments Database

    Seager, C. H.; Sinclair, M. B.; Mc Branch, D.; Heeger, A. J.; Baker, G. L.

    1991-01-01

    We have used the highly sensitive technique of Photothermal Deflection Spectroscopy (PDS) to measure changes in the infrared absorption spectra of MEHPPV, P3HT and Polydiacetylene-4BCMU induced by pumping these polymers with light above the {pi} - {pi}* transition energy. In contrast to previous chopped light transmission measurements of these effects, the PDS technique can directly measure the buildup or decay of the absorption coefficient, {alpha}, on the time scale of second to days. In the case of MEHPPV we observe that the time scale of seconds to days. In the case of MEHPPV we observe that above-gap light causes the appearance of a broad infrared peak in {alpha}, which continues to grow-in hours after the pump light is first applied. For this polymer the general shape of the absorption spectra in the unpumped state mimics the photo-induced changes, suggesting that remnant photo-induced states determine the maximum transparency observed under normal experimental conditions. For P3HT and to a lesser extent, MEHPPV, we also observe irreversible photo-induced absorption components which we tentatively identify with photo-induced oxidation of the polymer matrix.

  13. Electrocatalytic hydrogenation using precious metal microparticles in redox-active polymer films

    SciTech Connect

    Coche, L.; Ehui, B.; Limosin, D.; Moutet, J.C. )

    1990-11-09

    Glassy carbon felt electrodes have been modified by electrodeposition of poly(pyrrole-viologen) films (derived from N,N{prime}-dialkyl-4,4{prime}-bipyridinium salts), followed by electroprecipitation of precious metal (Pt, Pd, Rh, or Ru) microparticles. The resulting electrodes have been proved to be active for the electrocatalytic hydrogenation of conjugated enones (2-cyclohexen-1-one, cryptone, carvone, isophorone), styrene, and benzonitrile in aqueous media (pH 1). Despite low loadings of metal catalysts, high electric and products yields and a long term stability of these cathodes have been observed. The influence of the metal loading and the polymer structure on the catalytic efficiency as well as the selectivity obtained according to the metal catalyst used have been studied. Comparison with results previously reported for other catalytic cathodes like Pt/Pt, Pd/C, or Raney nickel electrodes proves the high efficiency of these metal microparticles within redox polymer film based electrodes.

  14. Optical Properties of Silver Particulate Films on Modified Polymer Substrates

    NASA Astrophysics Data System (ADS)

    Gurumurthy, S. C.; Pattabi, Manjunatha; Sanjeeva, Ganesh

    2011-07-01

    Results of the investigations carried out on the optical properties of particulate films deposited on 8 MeV electron beam irradiated polystyrene (PS) and on blends of PS and Poly (4-vinyl pyridine) (P4VP) are reported. It is observed that absorption maxima shift towards higher wavelength for films deposited on irradiated polystyrene and on blends of PS and P4VP. These results indicate that morphology of the particulate films can be changed by tuning the metal polymer interaction in an inert polymer through electron beam irradiation or by blending it with an interacting polymer like P4VP.

  15. Fluorine Substituted Conjugated Polymer of Medium Band Gap Yields 7% Efficiency in Polymer-Fullerene Solar Cells

    SciTech Connect

    Price, Samuel C.; Stuart, Andrew C.; Yang, Liqiang; Zhou, Huaxing; You, Wei

    2011-03-04

    Recent research advances on conjugated polymers for photovoltaic devices have focused on creating low band gap materials, but a suitable band gap is only one of many performance criteria required for a successful conjugated polymer. This work focuses on the design of two medium band gap (~2.0 eV) copolymers for use in photovoltaic cells which are designed to possess a high hole mobility and low highest occupied molecular orbital and lowest unoccupied molecular orbital energy levels. The resulting fluorinated polymer PBnDT-FTAZ exhibits efficiencies above 7% when blended with [6,6]-phenyl C61-butyric acid methyl ester in a typical bulk heterojunction, and efficiencies above 6% are still maintained at an active layer thicknesses of 1 μm. PBnDT-FTAZ outperforms poly(3-hexylthiophene), the current medium band gap polymer of choice, and thus is a viable candidate for use in highly efficient tandem cells. PBnDT-FTAZ also highlights other performance criteria which contribute to high photovoltaic efficiency, besides a low band gap.

  16. Fluorine Substituted Conjugated Polymer of Medium Band Gap Yields 7% Efficiency in Polymer-Fullerene Solar Cells

    SciTech Connect

    Price, Samuel C.; Stuart, Andrew C.; Yang, Liqiang; Zhou, Huaxing; You, Wei

    2011-03-30

    Recent research advances on conjugated polymers for photovoltaic devices have focused on creating low band gap materials, but a suitable band gap is only one of many performance criteria required for a successful conjugated polymer. This work focuses on the design of two medium band gap (~2.0 eV) copolymers for use in photovoltaic cells which are designed to possess a high hole mobility and low highest occupied molecular orbital and lowest unoccupied molecular orbital energy levels. The resulting fluorinated polymer PBnDT-FTAZ exhibits efficiencies above 7% when blended with [6,6]-phenyl C{sub 61}-butyric acid methyl ester in a typical bulk heterojunction, and efficiencies above 6% are still maintained at an active layer thicknesses of 1 μm. PBnDT-FTAZ outperforms poly(3-hexylthiophene), the current medium band gap polymer of choice, and thus is a viable candidate for use in highly efficient tandem cells. PBnDT-FTAZ also highlights other performance criteria which contribute to high photovoltaic efficiency, besides a low band gap.

  17. Fluorine substituted conjugated polymer of medium band gap yields 7% efficiency in polymer-fullerene solar cells.

    PubMed

    Price, Samuel C; Stuart, Andrew C; Yang, Liqiang; Zhou, Huaxing; You, Wei

    2011-03-30

    Recent research advances on conjugated polymers for photovoltaic devices have focused on creating low band gap materials, but a suitable band gap is only one of many performance criteria required for a successful conjugated polymer. This work focuses on the design of two medium band gap (~2.0 eV) copolymers for use in photovoltaic cells which are designed to possess a high hole mobility and low highest occupied molecular orbital and lowest unoccupied molecular orbital energy levels. The resulting fluorinated polymer PBnDT-FTAZ exhibits efficiencies above 7% when blended with [6,6]-phenyl C(61)-butyric acid methyl ester in a typical bulk heterojunction, and efficiencies above 6% are still maintained at an active layer thicknesses of 1 μm. PBnDT-FTAZ outperforms poly(3-hexylthiophene), the current medium band gap polymer of choice, and thus is a viable candidate for use in highly efficient tandem cells. PBnDT-FTAZ also highlights other performance criteria which contribute to high photovoltaic efficiency, besides a low band gap.

  18. RESEARCH ON THE ELECTRONIC AND OPTICAL PROPERTIES OF POLYMER AND OTHER ORGANIC MOLECULAR THIN FILMS

    SciTech Connect

    ALEXEI G. VITUKHNOVSKY; IGOR I. SOBELMAN - RUSSIAN ACADEMY OF SCIENCES

    1995-09-06

    Optical properties of highly ordered films of poly(p-phenylene) (PPP) on different substrates, thin films of mixtures of conjugated polymers, of fullerene and its composition with polymers, molecular J-aggregates of cyanine dyes in frozen matrices have been studied within the framework of the Agreement. Procedures of preparation of high-quality vacuum deposited PPP films on different substrates (ITO, Si, GaAs and etc.) were developed. Using time-correlated single photon counting technique and fluorescence spectroscopy the high quality of PPP films has been confirmed. Dependence of structure and optical properties on the conditions of preparation were investigated. The fluorescence lifetime and spectra of highly oriented vacuum deposited PPP films were studied as a function of the degree of polymerization. It was shown for the first time that the maximum fluorescence quantum yield is achieved for the chain length approximately equal to 35 monomer units. The selective excitation of luminescence of thin films of PPP was performed in the temperature range from 5 to 300 K. The total intensity of luminescence monotonically decreases with decreasing temperature. Conditions of preparation of highly cristallyne fullerene C{sub 60} films by the method of vacuum deposition were found. Composites of C{sub 60} with conjugated polymers PPV and polyacetylene (PA) were prepared. The results on fluorescence quenching, IR and resonant Raman spectroscopy are consistent with earlier reported ultrafast photoinduced electron transfer from PPV to C{sub 60} and show that the electron transfer is absent in the case of the PA-C{sub 60} composition. Strong quenching of PPV fluorescence was observed in the PPV-PA blends. The electron transfer from PPV to PA can be considered as one of the possible mechanisms of this quenching. The dynamics of photoexcitations in different types of J-aggregates of the carbocyanine dye was studied at different temperatures in frozen matrices. The optical

  19. Characterization of polymer films for use in bimorph chemical sensors

    NASA Astrophysics Data System (ADS)

    Chatzandroulis, S.; Goustouridis, D.; Raptis, I.

    2005-01-01

    In the present work white light interferometry is applied for the characterization of polymer films commonly used in bimorph chemical sensors. The study focuses on methacrylate polymers with positive tone patterning capabilities. The behavior upon exposure to controlled concentrations volatile organic compound and water vapors of thin poly (hydroxy ethyl methacrylate) (PHEMA) and poly (methyl methacrylate) (PMMA) layers was evaluated. The normalized film expansion for PHEMA, compared to PMMA, is higher in the case of water and methanol vapors, almost equal for ethanol and significantly lower in the case of acetone. This behavior could be attributed to the combination of polarity and hydrogen bonding capability of the analytes. A wide polymer film thickness range was examined and it was revealed that the normalized film expansion in both PHEMA and PMMA is nearly constant for films thicker than 100 nm and increases for thinner films.

  20. Study of (Cyclic Peptide)-Polymer Conjugate Assemblies by Small-Angle Neutron Scattering.

    PubMed

    Koh, Ming Liang; FitzGerald, Paul A; Warr, Gregory G; Jolliffe, Katrina A; Perrier, Sébastien

    2016-12-19

    We present a fundamental study into the self-assembly of (cyclic peptide)-polymer conjugates as a versatile supramolecular motif to engineer nanotubes with defined structure and dimensions, as characterised in solution using small-angle neutron scattering (SANS). This work demonstrates the ability of the grafted polymer to stabilise and/or promote the formation of unaggregated nanotubes by the direct comparison to the unconjugated cyclic peptide precursor. This ideal case permitted a further study into the growth mechanism of self-assembling cyclic peptides, allowing an estimation of the cooperativity. Furthermore, we show the dependency of the nanostructure on the polymer and peptide chemical functionality in solvent mixtures that vary in the ability to compete with the intermolecular associations between cyclic peptides and ability to solvate the polymer shell.

  1. Single particle and ensemble spectroscopy of conjugated polymer nanoparticles and their development for photodynamic therapy

    NASA Astrophysics Data System (ADS)

    Grimland, Jennifer L.

    Energy transport in conjugated polymers is the combination of energy transfer and exciton diffusion. There is considerable ongoing research in this field, converging to develop better organic photovoltaics, polymer light emitting diodes (PLEDs) and organic solar cells, to name a few. One way these phenomena can be explored is by doing solution dependent studies on conjugated polymer nanoparticles. With experiments on CP dots in an aqueous solution and the addition of a water miscible organic solvent in varying concentrations, dynamics occurring in the folding process can be better understood, and also exciton and fluorescence quenching properties can be extracted as a function of nanoparticle collapse. Steady state and time resolved fluorescence measurements were taken for two types of CP dots in bulk solution under varying solvent environments, including quantum yield, photobleaching and reversible photobleaching. The time-domain technique of time-correlated single photon counting (TCSPC) was used to determine excited state lifetimes and fluorescent decay traces. Simulating the TCSPC data provides insight on the relative number of quenchers that are observed by the polymer in each environment. In addition, single molecule fluorescence spectroscopy measurements were done on CP dots under varying solvent vapor atmospheres. Using the phenomenon of energy transfer, we have proven that doping the singlet oxygen photosensitizer tetraphenylporphyrin (TPP) into our conjugated polymer nanoparticles acts as an efficient and powerful photosensitizer for photodynamic therapy. The nanoparticles exhibit highly efficient collection of excitation light due to the large excitation cross-section of the polymer. A quantum efficiency of 0.5 was determined. Extraordinarily large cross-sections for two-photon absorption were found which is promising for near infrared multiphoton photodynamic therapy, and gel electrophoresis of DNA after irradiation in the presence of CP dots indicated

  2. Oxygen Radicals in Influenza-Induced Pathogenesis and Treatment with Pyran Polymer-Conjugated SOD

    NASA Astrophysics Data System (ADS)

    Oda, Tatsuya; Akaike, Takaaki; Hamamoto, Takayoshi; Suzuki, Fujio; Hirano, Takashi; Maeda, Hiroshi

    1989-05-01

    The pathogenicity of influenza virus infection in the mice involves, at least in part, overreaction of the immune responses of the host rather than a direct effect of virus multiplication. Xanthine oxidase, which is responsible for the generation of oxygen free radicals, was elevated in serum and lung tissue of mice infected with influenza virus. To test the theory that oxygen-free radicals are involved in pathogenesis, free radicals were removed by injecting superoxide dismutase (SOD), a specific superoxide radical scavenger, which was conjugated with a pyran copolymer. The conjugate protected mice against a potentially lethal influenza virus infection if administered 5 to 8 days after infection. These findings indicate that oxygen radicals are important in the pathogenesis of influenza virus infection, and that a polymer-conjugated SOD has therapeutic potential for this virus infection and other diseases associated with free radicals.

  3. High-mobility n-type conjugated polymers based on electron-deficient tetraazabenzodifluoranthene diimide for organic electronics.

    PubMed

    Li, Haiyan; Kim, Felix Sunjoo; Ren, Guoqiang; Jenekhe, Samson A

    2013-10-09

    High-mobility p-type and ambipolar conjugated polymers have been widely reported. However, high-mobility n-type conjugated polymers are still rare. Herein we present poly(tetraazabenzodifluoranthene diimide)s, PBFI-T and PBFI-BT, which exhibit a novel two-dimensional (2D) π-conjugation along the main chain and in the lateral direction, leading to high-mobility unipolar n-channel transport in field-effect transistors. The n-type polymers exhibit electron mobilities of up to 0.30 cm(2)/(V s), which is among the highest values for unipolar n-type conjugated polymers. Complementary inverters incorporating n-channel PBFI-T transistors produced nearly perfect switching characteristics with a high gain of 107.

  4. Stimulation of immune systems by conjugated polymers and their potential as an alternative vaccine adjuvant

    NASA Astrophysics Data System (ADS)

    Gong, Hua; Xiang, Jian; Xu, Ligeng; Song, Xuejiao; Dong, Ziliang; Peng, Rui; Liu, Zhuang

    2015-11-01

    Recently, conjugated polymers have been widely explored in the field of nanomedicine. Careful evaluations of their biological effects are thus urgently needed. Hereby, we systematically evaluated the biological effects of different types of conjugated polymers on macrophages and dendritic cells (DCs), which play critical roles in the innate and adaptive immune systems, respectively. While naked poly-(3,4-ethylenedioxythiophene):poly(4-styrenesulfonate) (PEDOT:PSS) exhibits a high level of cytotoxicity, polyethylene glycol (PEG) modified PEDOT:PSS (PEDOT:PSS-PEG) shows greatly reduced toxicity to various types of cells. To our surprise, PEGylation of PEDOT:PSS could obviously enhance the cellular uptake of these nanoparticles, leading to subsequent immune stimulations of both macrophages and DCs. In contrast, another type of conjugated polymer, polypyrrole (PPy), is found to be an inert material with neither significant cytotoxicity nor noticeable immune-stimulation activity. Interestingly, utilizing ovalbumin (OVA) as a model antigen, it is further uncovered in our ex vivo experiment that PEDOT:PSS-PEG may serve as an adjuvant to greatly enhance the immunogenicity of OVA upon simple mixing. Our study on the one hand suggests the promise of developing novel nano-adjuvants based on conjugated polymers, and on the other hand highlights the importance of careful evaluations of the impacts of any new nanomaterials developed for nanomedicine on the immune systems.Recently, conjugated polymers have been widely explored in the field of nanomedicine. Careful evaluations of their biological effects are thus urgently needed. Hereby, we systematically evaluated the biological effects of different types of conjugated polymers on macrophages and dendritic cells (DCs), which play critical roles in the innate and adaptive immune systems, respectively. While naked poly-(3,4-ethylenedioxythiophene):poly(4-styrenesulfonate) (PEDOT:PSS) exhibits a high level of cytotoxicity

  5. Targeted conjugation of breast anticancer drug tamoxifen and its metabolites with synthetic polymers.

    PubMed

    Sanyakamdhorn, S; Agudelo, D; Bekale, L; Tajmir-Riahi, H A

    2016-09-01

    Conjugation of antitumor drug tamoxifen and its metabolites, 4-hydroxytamxifen and ednoxifen with synthetic polymers poly(ethylene glycol) (PEG), methoxypoly (ethylene glycol) polyamidoamine (mPEG-PAMAM-G3) and polyamidoamine (PAMAM-G4) dendrimers was studied in aqueous solution at pH 7.4. Multiple spectroscopic methods, transmission electron microscopy (TEM) and molecular modeling were used to characterize the drug binding process to synthetic polymers. Structural analysis showed that drug-polymer binding occurs via both H-bonding and hydrophobic contacts. The order of binding is PAMAM-G4>mPEG-PAMAM-G3>PEG-6000 with 4-hydroxttamoxifen forming more stable conjugate than tamoxifen and endoxifen. Transmission electron microscopy showed significant changes in carrier morphology with major changes in the shape of the polymer aggregate as drug encapsulation occurred. Modeling also showed that drug is located in the surface and in the internal cavities of PAMAM with the free binding energy of -3.79 for tamoxifen, -3.70 for 4-hydroxytamoxifen and -3.69kcal/mol for endoxifen, indicating of spontaneous drug-polymer interaction at room temperature.

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

    NASA Astrophysics Data System (ADS)

    Li, Xiao-xue; Chen, Gang

    2017-02-01

    Based on the one-dimensional extended Su-Schrieffer-Heeger model, we theoretically investigate the effect of interchain coupling on the formation and polarization of the single-excited state of polaron in conjugated polymers. It is found that there exists a turnover value of the coupling strength, over which the excited polaron could not be formed in either of the two coupled chains. Instead, a polaron-like particle is localized at the center of each chain. In addition, we also find that the reverse polarization of the excited polaron could be enhanced for some cases in polymer when the interchain coupling becomes strong until it exceeds the critical value.

  7. Theory of Exciton Migration and Field-Induced Dissociation in Conjugated Polymers

    NASA Astrophysics Data System (ADS)

    Vissenberg, M. C. J. M.; de Jong, M. J. M.

    1996-12-01

    The interplay of migration, recombination, and dissociation of excitons in disordered media is studied theoretically in the low temperature regime. An exact expression for the photoluminescence spectrum is obtained. The theory is applied to describe the electric field-induced photoluminescence-quenching experiments by Kersting et al. [Phys. Rev. Lett. 73, 1440 (1994)] and Deussen et al. [Synth. Met. 73, 123 (1995)] on conjugated polymer systems. Good agreement with experiment is obtained using an on-chain dissociation mechanism, which implies a separation of the electron-hole pair along the polymer chain.

  8. Acoustical performance of an electrostrictive polymer film loudspeaker

    PubMed

    Heydt; Pelrine; Joseph; Eckerle; Kornbluh

    2000-02-01

    A new type of loudspeaker that generates sound by means of the electrostrictive response of a thin polymer film is described. Electrostrictive polymer film (EPF) loudspeakers are constructed with inexpensive, lightweight materials and have a very low profile. The films are typically silicone and are coated with compliant electrodes to allow large film deformations. Acoustical frequency response measurements from 5 x 5 cm (planar dimensions) prototype EPF loudspeakers are presented. Measurements of harmonic distortion are also shown, along with results demonstrating reduced harmonic distortion achieved with square-root wave shaping. Applications of EPF loudspeakers include active noise control and general-purpose flat-panel loudspeakers.

  9. Precise Side-Chain Engineering of Thienylenevinylene-Benzotriazole-Based Conjugated Polymers with Coplanar Backbone for Organic Field Effect Transistors and CMOS-like Inverters.

    PubMed

    Lee, Min-Hye; Kim, Juhwan; Kang, Minji; Kim, Jihong; Kang, Boseok; Hwang, Hansu; Cho, Kilwon; Kim, Dong-Yu

    2017-01-25

    Two donor-acceptor (D-A) alternating conjugated polymers based on thienylenevinylene-benzotriazole (TV-BTz), PTV6B with a linear side chain and PTVEhB with a branched side chain, were synthesized and characterized for organic field effect transistors (OFETs) and complementary metal-oxide-semiconductor (CMOS)-like inverters. According to density functional theory (DFT), polymers based on TV-BTz exhibit a coplanar and rigid structure with no significant twists, which could cause to an increase in charge-carrier mobility in OFETs. Alternating alkyl side chains of the polymers impacted neither the band gap nor the energy level. However, it significantly affected the morphology and crystallinity when the polymer films were thermally annealed. To investigate the effect of thermal annealing on the morphology and crystallinity, we characterized the polymer films using atomic force microscopy (AFM) and 2D-grazing incidence X-ray diffraction (2D-GIWAXD). Fibrillary morphologies with larger domains and increased crystallinity were observed in the polymer films after thermal annealing. These polymers exhibited improved charge-carrier mobilities in annealed films at 200 °C and demonstrated optimal OFET device performance with p-type transport characteristics with charge-carrier mobilities of 1.51 cm(2)/(V s) (PTV6B) and 2.58 cm(2)/(V s) (PTVEhB). Furthermore, CMOS-like inorganic (ZnO)-organic (PTVEhB) hybrid bilayer inverter showed that the inverting voltage (Vinv) was positioned near the ideal switching point at half (1/2) of supplied voltage (VDD) due to fairly balanced p- and n-channels.

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

    PubMed

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

    2011-12-08

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

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

    SciTech Connect

    Dixit, S.N. ); Guo, D.; Mazumdar, S. . 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.

  12. Alpha-methylprednisolone conjugated cyclodextrin polymer-based nanoparticles for rheumatoid arthritis therapy.

    PubMed

    Hwang, Jungyeon; Rodgers, Kathleen; Oliver, James C; Schluep, Thomas

    2008-01-01

    A glycinate derivative of alpha-methylprednisolone (MP) was prepared and conjugated to a linear cyclodextrin polymer (CDP) with a loading of 12.4% w/w. The polymer conjugate (CDP-MP) self-assembled into nanoparticles with a size of 27 nm. Release kinetics of MP from the polymer conjugate showed a half-life (t1/2) of 50 h in phosphate buffer solution (PBS) and 19 h in human plasma. In vitro, the proliferation of human lymphocytes was suppressed to a similar extent but with a delayed effect when CDP-MP was compared with free MP. In vivo, CDP-MP was administered intravenously to mice with collagen-induced arthritis and compared with free MP. CDP-MP was administered weekly for six weeks (0.07, 0.7, and 7 mg/kg/week) and MP was administered daily for six weeks (0.01, 0.1, and 1 mg/kg/day). Body weight changes were minimal in all animals. After 28 days, a significant decrease in arthritis score was observed in animals treated weekly with an intermediate or high dose of CDP-MP. Additionally, dorsoplantar swelling was reduced to baseline in animals treated with CDP-MP at the intermediate and high dose level. Histological evaluation showed a reduction in synovitis, pannus formation and disruption of architecture at the highest dose level of CDP-MP. MP administered daily at equivalent cumulative doses showed minimal efficacy in this model. This study demonstrates that conjugation of MP to a cyclodextrin-polymer may improve its efficacy, leading to lower doses and less frequent administration for a safer and more convenient management of rheumatoid arthritis.

  13. Broadband optical limiting and nonlinear optical absorption properties of a novel hyperbranched conjugated polymer

    NASA Astrophysics Data System (ADS)

    Li, Chao; Liu, Chunling; Li, Quanshui; Gong, Qihuang

    2004-12-01

    The nonlinear transmittance of a novel hyperbranched conjugated polymer named DMA-HPV has been measured in CHCl 3 solution using a nanosecond optical parametric oscillator. DMA-HPV shows excellent optical limiting performance in the visible region from 490 to 610 nm. An explanation based on the combination of two-photon absorption and reverse saturable absorption was proposed for its huge and broadband nonlinear optical absorption.

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

    SciTech Connect

    Partee, Jonathan

    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.

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

    PubMed

    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.

  16. Synthesis and evaluation of optical and electrochemical properties of a new conjugated polymer containing substituted thiophene and non-conjugation linkers

    NASA Astrophysics Data System (ADS)

    R, Prashanth Kumar K.; D, Udayakumar; K, Siji Narendran N.; K, Chandrasekharan

    2014-10-01

    Conjugated polymers have been developed in a variety of applied fields owing to their promising optoelectronic properties. These are pursuing considerable interest as opto-electrical material because of their chemical stability and processability. This paper describes the synthesis and study of electro-optical properties of a new donoracceptor polymer composed of substituted thiophene and 4,4'-propane-2,2-diyldiphenol units as electron rich moieties and 1,3,4-oxadiazole unit as electron deficient moiety. The optical properties of the polymer are studied using UV-visible absorption spectroscopy and fluorescent emission spectroscopy. From the electrochemical data, HOMO and LUMO energy levels of the polymer are calculated.

  17. Self-lubricating polymer composites and polymer transfer film lubrication for space applications

    NASA Technical Reports Server (NTRS)

    Fusaro, Robert L.

    1990-01-01

    The use of self-lubricating polymers and polymer composites in space is somewhat limited today. In general, they are only used when other methods are inadequate. There is potential, however, for these materials to make a significant impact on future space missions if properly utilized. Some of the different polymers and fillers used to make self-lubricating composites are surveyed. The mechanisms of composite lubrication and wear, the theory behind transfer film lubricating mechanisms, and some factors which affect polymer composite wear and transfer are examined. In addition, some of the current space tribology application areas for self-lubricating polymer composites and polymer transfer are mentioned.

  18. Signal amplification in immunohistochemistry: loose-jointed deformable heteropolymeric HRP conjugates vs. linear polymer backbone HRP conjugates.

    PubMed

    Buchwalow, Igor; Boecker, Werner; Wolf, Eduard; Samoilova, Vera; Tiemann, Markus

    2013-07-01

    Improvements in reagents and protocols for immunohistochemistry have led to increased sensitivity of detection systems. A significant level of signal amplification was achieved by the chain-polymer conjugate technology utilizing enzyme-labeled inert "backbone" molecule of dextran (Dako). However, the relatively large size of the dextran molecule in aqueous phase appears to create spatial hindrance compromising the penetrative ability of the detection reagent. Novel AmpliStain™ detection systems (SDT GmbH, Baesweiler, Germany) seem to overcome these constraints offering a more compact and deformable conjugate design that facilitates agile penetration through the narrowest diffusion pathways in tissue sections. Here, we compared the level of signal amplification achievable with AmpliStain™-HRP (SDT) and EnVision™+-HRP (Dako). Our results show that the AmpliStain™-HRP systems allow higher dilutions of primary antibodies in both immunohistochemistry and ELISA. Compared with EnVision™+, anti-mouse AmpliStain™ enables at least three times more sensitive detection of mouse antibodies, whereas anti-rabbit AmpliStain™ is ten times more sensitive than anti-rabbit EnVision™+.

  19. Narrow band gap conjugated polymers for emergent optoelectronic technologies

    NASA Astrophysics Data System (ADS)

    Azoulay, Jason D.; Zhang, Benjamin A.; London, Alexander E.

    2015-09-01

    Conjugated organic molecules effectively produce and harvest visible light and find utility in a variety of emergent optoelectronic technologies. There is currently interest in expanding the scope of these materials to extend functionality into the infrared (IR) spectral regions and endow functionality relevant in emergent technologies. Developing an understanding of the interplay between chemical and electronic structure in these systems will require control of the frontier orbital energetics (separation, position, and alignment), ground state electronic configurations, interchain arrangements, solid-state properties, and many other molecular features with synthetic precision that has yet to be demonstrated. Bridgehead imine substituted 4H-cyclopenta[2,1-b:3,4-b']dithiophene (CPDT) structural units, in combination with strong acceptors with progressively delocalized π-systems, afford modular donor-acceptor copolymers with broad and long wavelength absorption that spans technologically relevant wavelength (λ) ranges from 0.7 < λ < 3.2 μm.1 Here we demonstrate that electronic and structural manipulation play a major role in influencing the energetics of these systems and ultimately controlling the band gap of the materials. These results bear implication in the development of very narrow band gap systems where precise control will be necessary for achieving desired properties such as interactions with longer wavelength light.

  20. Elements of adaptive optics based on metallized polymer films

    NASA Astrophysics Data System (ADS)

    Voliak, T. B.; Krasiuk, I. K.; Pashinin, P. P.

    Results of an experimental study of the stability of metallized polymer films exposed to laser radiation at wavelengths of 1.06 and 10.6 microns are reported, and methods for fabricating variable-curvature mirrors from these films are discussed. Formulas are presented for calculating the shape of film mirrors as a function of the pressure acting on the film, mounting contour, and film properties. The performance of film mirrors is investigated experimentally in a pulsed CO2 laser with stable and unstable resonators.

  1. Development of polymer film solar collectors: A status report

    NASA Astrophysics Data System (ADS)

    Wilhelm, W. G.; Andrews, J. W.

    1982-08-01

    Solar energy collector panels using polymer film and laminate technology were developed which demonstrate low cost and high thermal performance for residential and commercial applications. This device uses common water in the absorber/heat exchanger which is constructed with polymer film adhesively laminated to aluminum foil as the outer surfaces. Stressed polymer films are also used for the outer window and back surface of the panel forming a high strength structural composite. Rigid polymer foam complements the design by contributing insulation and structural definition. This design resulted in very low weight (3.5 kg/m(2)), potentially very low manufacturing cost (aprox. $11/m(2)), and high thermal performance. The development of polymer materials for this technology will be a key to early commercial success.

  2. Dispersing nanoparticles in a polymer film via solvent evaporation

    SciTech Connect

    Cheng, Shengfeng; Grest, Gary S.

    2016-05-19

    Large-scale molecular dynamics simulations are used to study the dispersion of nanoparticles (NPs) in a polymer film during solvent evaporation. As the solvent evaporates, a dense polymer-rich skin layer forms at the liquid/vapor interface, which is either NP rich or poor depending on the strength of the NP/polymer interaction. When the NPs are strongly wet by the polymer, the NPs accumulate at the interface and form layers. However, when the NPs are only partially wet by the polymer, most NPs are uniformly distributed in the bulk of the polymer film, with the dense skin layer serving as a barrier to prevent the NPs from moving to the interface. Furthermore, our results point to a possible route to employ less favorable NP/polymer interactions and fast solvent evaporation to uniformly disperse NPs in a polymer film, contrary to the common belief that strong NP/polymer attractions are needed to make NPs well dispersed in polymer nanocomposites.

  3. Dispersing nanoparticles in a polymer film via solvent evaporation

    DOE PAGES

    Cheng, Shengfeng; Grest, Gary S.

    2016-05-19

    Large-scale molecular dynamics simulations are used to study the dispersion of nanoparticles (NPs) in a polymer film during solvent evaporation. As the solvent evaporates, a dense polymer-rich skin layer forms at the liquid/vapor interface, which is either NP rich or poor depending on the strength of the NP/polymer interaction. When the NPs are strongly wet by the polymer, the NPs accumulate at the interface and form layers. However, when the NPs are only partially wet by the polymer, most NPs are uniformly distributed in the bulk of the polymer film, with the dense skin layer serving as a barrier tomore » prevent the NPs from moving to the interface. Furthermore, our results point to a possible route to employ less favorable NP/polymer interactions and fast solvent evaporation to uniformly disperse NPs in a polymer film, contrary to the common belief that strong NP/polymer attractions are needed to make NPs well dispersed in polymer nanocomposites.« less

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

    PubMed

    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 712m(2)g(-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 2.08×10(3)Lmol(-1) and a detection limit of 7.22×10(-7)molL(-1) (0.165mgL(-1)). In short, the DTF may be a new kind of fluorescence sensing material for detecting TNP.

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

    PubMed

    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.

  6. Bioreducible polymer-conjugated oncolytic adenovirus for hepatoma-specific therapy via systemic administration.

    PubMed

    Kim, Pyung-Hwan; Kim, Jaesung; Kim, Tae-il; Nam, Hye Yeong; Yockman, James W; Kim, Minjung; Kim, Sung Wan; Yun, Chae-Ok

    2011-12-01

    Systemic administration of adenovirus (Ad) vectors is complicated by host immune responses and viral accumulation in the liver, resulting in a short circulatory virus half-life, low efficacy, and host side effects. Ad surface modification is thus required to enhance safety and therapeutic efficacy. An arginine-grafted bioreducible polymer (ABP) was chemically conjugated to the Ad surface, generating Ad-ΔE1/GFP-ABP. A hepatocellular carcinoma [HCC]-selective oncolytic Ad complex, YKL-1001-ABP, was also generated. Transduction efficiency of Ad-ΔE1/GFP-ABP was enhanced compared to naked Ad-ΔE1/GFP. YKL-1001-ABP elicited an enhanced and specific killing effect in liver cancer cells (Huh7 and HepG2) expressing α-fetoprotein (AFP). Compared with naked Ad, systemic administration of ABP-conjugated Ad resulted in reduced liver toxicity and interleukin (IL)-6 production in vitro and in vivo. Ad-ΔE1/GFP-ABP was more resistant to the neutralizing effects of human serum compared to naked Ad-ΔE1/GFP. ABP conjugation extended blood circulation time 45-fold and reduced anti-Ad Ab neutralization. Moreover, systemic administration of YKL-1001-ABP markedly suppressed growth of Huh7 hepatocellular carcinoma. These results demonstrate that chemical conjugation of ABP to the Ad surface improves safety and efficacy, indicating that ABP-conjugated Ad is a potentially useful cancer therapeutic agent to target cancer via systemic administration.

  7. Dibenzopyran-Based Wide Band Gap Conjugated Copolymers: Structural Design and Application for Polymer Solar Cells.

    PubMed

    Zhou, Yuanyuan; Li, Miao; Guo, Yijing; Lu, Heng; Song, Jinsheng; Bo, Zhishan; Wang, Hua

    2016-11-16

    With the efficient synthesis of the crucial dibenzopyran building block, a series of PDBPTBT polymers containing different alkyl side chains and/or fluorine substitution were designed and synthesized via the microwave-assisted Suzuki polycondensation. Quantum chemistry calculations based on density functional theory indicated that different substitutions have significant impacts on the planarity and rigidity of the polymer backbones. Interestingly, the alkyloxy chains of PDBPTBT-4 tend to stay in the same plane with the benzothiadiazole unit, but the others appear to be out of plane. With the S···O and F···H/F···S supramolecular interactions, the conformations of the four polymers will be locked in different ways as predicted by the quantum chemistry calculation. Such structural variation resulted in varied solid stacking and photophysical properties as well as the final photovoltaic performances. Conventional devices based on these four polymers were fabricated, and PDBPTBT-5 displayed the best PCE of 5.32%. After optimization of the additive types, ratios, and the interlayers at the cathode, a high PCE of 7.06% (Voc = 0.96 V, Jsc = 11.09 mA/cm(2), and FF = 0.67) is obtained for PDBPTBT-5 with 2.0% DIO as the additive and PFN-OX as the electron-transporting layer. These results indicated DBP-based conjugated polymers are promising wide band gap polymer donors for high-efficiency polymer solar cells.

  8. The Miscibility of PCBM in Low Band-Gap Conjugated Polymers in Organic Photovoltaics

    NASA Astrophysics Data System (ADS)

    Chen, Huipeng; You, Wei; Peet, Jeff; Azoulay, Jason; Bazan, Guillermo; Dadmun, Mark

    2012-02-01

    Understanding the morphology of the photoactive layer in organic photovoltaics (OPVs) is essential to optimizing conjugated polymer-based solar cells to meet the targeted efficiency of 10%. The miscibility and interdiffusion of components are among the key elements that impact the development of morphology and structure in OPV active layers. This study uses neutron reflectivity to correlate the structure of low band gap polymers to their miscibility with PCBM. Several low band gap polymers that exhibit power conversion efficiencies exceeding 7%, including PBnDT-DTffBT were examined. The intermixing of low band-gap polymer and PCBM bilayers was monitored by neutron reflectivity before and after thermal annealing, providing quantification of the miscibility and interdiffusion of PCBM within the low band gap polymer layer. These results indicate that the miscibility of PCBM ranges from 3% to 26% with the low band-gap polymers studied. The correlation between low band gap polymer structure and miscibility of PCBM will also be discussed.

  9. Engineering curvature in graphene ribbons using ultrathin polymer films.

    PubMed

    Li, Chunyu; Koslowski, Marisol; Strachan, Alejandro

    2014-12-10

    We propose a method to induce curvature in graphene nanoribbons in a controlled manner using an ultrathin thermoset polymer in a bimaterial strip setup and test it via molecular dynamics (MD) simulations. Continuum mechanics shows that curvature develops to release the residual stress caused by the chemical and thermal shrinkage of the polymer during processing and that this curvature increases with decreasing film thickness; however, significant deformation is only achieved for ultrathin polymer films. Quite surprisingly, explicit MD simulations of the curing and annealing processes show that the predicted trend not just continues down to film thicknesses of 1-2 nm but that the curvature development is enhanced significantly in such ultrathin films due to surface tension effects. This combination of effects leads to very large curvatures of over 0.14 nm(-1) that can be tuned via film thickness. This provides a new avenue to engineer curvature and, thus, electromagnetic properties of graphene.

  10. Rapid synthesis of flexible conductive polymer nanocomposite films

    NASA Astrophysics Data System (ADS)

    Blattmann, C. O.; Sotiriou, G. A.; Pratsinis, S. E.

    2015-03-01

    Polymer nanocomposite films with nanoparticle-specific properties are sought out in novel functional materials and miniaturized devices for electronic and biomedical applications. Sensors, capacitors, actuators, displays, circuit boards, solar cells, electromagnetic shields and medical electrodes rely on flexible, electrically conductive layers or films. Scalable synthesis of such nanocomposite films, however, remains a challenge. Here, flame aerosol deposition of metallic nanosliver onto bare or polymer-coated glass substrates followed by polymer spin-coating on them leads to rapid synthesis of flexible, free-standing, electrically conductive nanocomposite films. Their electrical conductivity is determined during their preparation and depends on substrate composition and nanosilver deposition duration. Accordingly, thin (<500 nm) and flexible nanocomposite films are made having conductivity equivalent to metals (e.g. 5 × 104 S cm-1), even during repetitive bending.

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

    PubMed

    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.

  12. Charge carrier mobility in conjugated organic polymers: simulation of an electron mobility in a carbazole-benzothiadiazole-based polymer

    NASA Astrophysics Data System (ADS)

    Li, Yaping; Lagowski, Jolanta B.

    2011-08-01

    Inorganic (mostly silicon based) solar cells are important devices that are used to solve the world energy and environmental needs. Now days, organic solar cells are attracting considerable attention in the field of photovoltaic cells because of their low cost and processing flexibility. Often conjugated polymers are used in the construction of the organic solar cells. We study the conjugated polymers' charge transport using computational approach that involves the use of the density functional theory (DFT), semiempirical (ZINDO), and Monte Carlo (MC) theoretical methods in order to determine their transfer integrals, reorganization energies, transfer rates (with the use of Marcus-Hush equation) and mobilities. We employ the experimentally determined three dimensional (3D) structure of poly(9,9'-di-n-octylfluorene-alt-benzothiadiazole) (F8BT) to estimate the electron mobility in a similar co-alternating polymer consisting of carbazole and benzothiadiazole units (C8BT). In agreement with our previous work, we found that including an orientational disorder in the crystal reduces the electron mobility in C8BT. We hope that the proposed computational approach can be used to predict charge mobility in organic materials that are used in solar cells.

  13. Pulsed DC discharge for synthesis of conjugated plasma polymerized aniline thin film

    NASA Astrophysics Data System (ADS)

    Barman, Tapan; Pal, Arup R.

    2012-10-01

    The polymerization of aniline in pulsed dc plasma is studied and the effects of variation of pressure, power, frequency and duty cycle on the chemical structure of the obtained film are examined. During the film deposition optical emission spectroscopy is used to investigate the molecular dissociation of aniline. The chemical structure of the films is characterized using Fourier transform infra-red spectroscopy. The surface morphology is studied using atomic force microscopy. Results show the retention of polyaniline like structure having conjugated nature at some particular discharge conditions. Moreover, it is observed that a strong dependence of film chemistry is obvious on the discharge power, reactor pressure, pulse repetition frequency and duty cycle. The advantages of the pulsed dc for deposition of conjugated plasma polymerizes thin film have been highlighted.

  14. Interfacial exciplex formation in bilayers of conjugated polymers

    NASA Astrophysics Data System (ADS)

    Nobuyasu, R. S.; Araujo, K. A. S.; Cury, L. A.; Jarrosson, T.; Serein-Spirau, F.; Lère-Porte, J.-P.; Dias, F. B.; Monkman, A. P.

    2013-10-01

    The donor-acceptor interactions in sequential bilayer and blend films are investigated. Steady-state and time-resolved photoluminescence (PL) were measured to characterize the samples at different geometries of photoluminescence collection. At standard excitation, with the laser incidence at 45° of the normal direction of the sample surface, a band related to the aggregate states of donor molecules appears for both blend and bilayer at around 540 nm. For the PL spectra acquired from the edge of the bilayer, with the laser incidence made at normal direction of the sample surface (90° geometry), a new featureless band emission, red-shifted from donor and acceptor emission regions was observed and assigned as the emission from interfacial exciplex states. The conformational complexity coming from donor/acceptor interactions at the heterojunction interface of the bilayer is at the origin of this interfacial exciplex emission.

  15. Polymer Wall Formation Using Liquid-Crystal/Polymer Phase Separation Induced on Patterned Polyimide Films

    NASA Astrophysics Data System (ADS)

    Murashige, Takeshi; Fujikake, Hideo; Sato, Hiroto; Kikuchi, Hiroshi; Kurita, Taiichiro; Sato, Fumio

    2004-12-01

    We could form lattice-shaped polymer walls in a liquid crystal (LC) layer through the thermal phase separation of an LC/polystyrene solution between substrates with polyimide films etched by short-wavelength ultraviolet irradiation using a photomask. The LC wetting difference between the polyimide and substrate surfaces caused the coalescence of growing LC droplets on patterned polyimide films with the progress of phase separation. Consequently, polymer walls were formed on substrate surface areas without polyimide films. The shape of the polymer wall formed became sharp with the use of rubbed polyimide films because the nucleation of growing LC droplets concentrated on the patterned polyimide films. It is thought that the increase in the alignment order of LC molecules in the solution near the rubbed polyimide films promotes the formation of LC molecular aggregation, which becomes the growth nuclei of LC droplets.

  16. Stress effects in prism coupling measurements of thin polymer films

    NASA Astrophysics Data System (ADS)

    Agan, S.; Ay, F.; Kocabas, A.; Aydinli, A.

    2005-02-01

    Due to the increasingly important role of some polymers in optical waveguide technologies, precise measurement of their optical properties has become important. Typically, prism coupling to slab waveguides made of materials of interest is used to measure the relevant optical parameters. However, such measurements are often complicated by the softness of the polymer films when stress is applied to the prism to couple light into the waveguides. In this work, we have investigated the optical properties of three different polymers, polystyrene (PS), polymethyl-methacrylate (PMMA), and benzocyclobutane (BCB). For the first time, the dependence of the refractive index, film thickness, and birefringence on applied stress in these thin polymer films was determined by means of the prism coupling technique. Both symmetric trapezoid shaped and right-angle prisms were used to couple the light into the waveguides. It was found that trapezoid shaped prism coupling gives better results in these thin polymer films. The refractive index of PMMA was found to be in the range of 1.4869 up to 1.4876 for both TE and TM polarizations under the applied force, which causes a small decrease in the film thickness of up to 0.06 μm. PMMA waveguide films were found not to be birefringent. In contrast, both BCB and PS films exhibit birefringence albeit of opposing signs.

  17. How Many Parameters Actually Affect the Mobility of Conjugated Polymers?

    NASA Astrophysics Data System (ADS)

    Fornari, Rocco P.; Blom, Paul W. M.; Troisi, Alessandro

    2017-02-01

    We describe charge transport along a polymer chain with a generic theoretical model depending in principle on tens of parameters, reflecting the chemistry of the material. The charge carrier states are obtained from a model Hamiltonian that incorporates different types of disorder and electronic structure (e.g., the difference between homo- and copolymer). The hopping rate between these states is described with a general rate expression, which contains the rates most used in the literature as special cases. We demonstrate that the steady state charge mobility in the limit of low charge density and low field ultimately depends on only two parameters: an effective structural disorder and an effective electron-phonon coupling, weighted by the size of the monomer. The results support the experimental observation [N. I. Craciun, J. Wildeman, and P. W. M. Blom, Phys. Rev. Lett. 100, 056601 (2008), 10.1103/PhysRevLett.100.056601] that the mobility in a broad range of (polymeric) semiconductors follows a universal behavior, insensitive to the chemical detail.

  18. Multicolor Luminescence from Conjugates of Genetically Encoded Elastin-like Polymers and Terpyridine-Lanthanides

    DOE PAGES

    Ghosh, Koushik; Balog, Eva Rose M.; Kahn, Jennifer L.; ...

    2015-08-20

    Functional hybrid materials with optically active metal-ligand moieties embedded within a polymer matrix have a great potential in (bio)materials science, including applications in light-emitting diode devices. Here, we report a simple strategy to incorporate terpyridine derivatives into the side chains of elastin-like polymers (ELPs). The further binding of trivalent lanthanide ions with the terpyridine ligands generated an array of photoluminescence ranging from the visible to the near-infrared regions. Lastly, as thin films, these ELP-based optical materials also exhibited distinct morphologies that depend upon the temperature of the aqueous solutions from which the hybrid polymers were spin coated or drop cast.

  19. Adhesion of metals to spin-coated fluorocarbon polymer films

    NASA Astrophysics Data System (ADS)

    Kim, Yong-Kil; Chang, Chin-An; Schrott, A. G.

    1990-01-01

    Adhesion between metals and fluorocarbon polymer films has been studied for Cu, Cr, Ti, Al, and Au on polytetrafluoroethylene (PTFE) and tetrafluoroethylene-hexafluoropropylene copolymer (FEP) films. Polymer films were applied on the Cr/SiO2 /Si substrate by spinning the aqueous dispersions of the polymer resin particles, followed by thermal curing. Strips of different metals were deposited on the polymers, and adhesion was measured at 90° peel test. The peel strengths were invariably higher for the metals on FEP than those of the corresponding metals on PTFE. Among the metals, Ti showed the highest peel strength for both polymers, followed by Cr and Al, with Cu and Au being the lowest. The peel strengths of Ti, Cr, and Cu on FEP are 85, 45, and 12 g/mm, respectively, and the corresponding ones on PTFE are 23, 5, and 2 g/mm, respectively. X-ray photoelectron spectroscopic analysis shows that the metal-polymer bonding involves the metal-carbon interactions. The strongest interaction is observed for Ti with the polymers, forming Ti carbidelike bonds. Cr also shows strong interaction with the two polymers, but to a lesser degree compared with Ti. Only a weak bonding is shown for Cu. The difference in peel strengths among the metals shows a correlation with the difference in electronegativities between the metals and carbon. Little contribution to the observed peel strengths is seen from the surface morphological analysis of the untreated polymers.

  20. Fracture and fatigue of ultrathin nanoporous polymer films

    NASA Astrophysics Data System (ADS)

    Kearney, Andrew V.

    Nanoporous polymer layers are being considered for a range of emerging nanoscale applications, from low permittivity materials for interlayer dielectrics in microelectronics and anti-reflective coatings in optical technologies, to biosensors and size-selective membranes for biological applications. Polymer thin films have inherently low elastic modulus, strength and hardness, but exhibit fracture properties that are higher than those reported for glass, ceramic, and even some metal layers. However, constraint of a ductile polymer between two elastic layers is expected to affect the local plasticity ahead of a crack tip and its contribution to the film adhesion with films below a micron in thickness. Additionally, nanoporosity would be expected to have a deleterious effect on mechanical properties, producing materials and layers that are structurally weaker than fully dense versions they replace. Therefore, the integration of these nanoporous polymer layer at nanometer thicknesses would present significantly processing and mechanical reliability challenges. In this dissertation, surprising evidence is presented that nanoporous polymer films exhibit increasing fracture energy with increasing porosity. Such behavior is in stark contrast to a wide range of reported behavior for porous solids. A ductile nano-void growth and coalescence fracture mechanics-based model is presented to rationalize the increase in fracture toughness of the voided polymer film. The model is shown to explain the behavior in terms of a specific scaling of the size of the pores with pore volume fraction. It is demonstrated that the pore size must increase with close to a linear dependence on the volume fraction in order to increase rather than decrease the fracture energy. Independent characterization of the pore size as a function of volume fraction is shown to confirm predictions made by the model. The fracture behavior of these constrained polymer films are also examined with film thickness

  1. Special Polymer/Carbon Composite Films for Detecting SO2

    NASA Technical Reports Server (NTRS)

    Homer, Margie; Ryan, Margaret; Yen, Shiao-Pin; Kisor, Adam; Jewell, April; Shevade, Abhijit; Manatt, Kenneth; Taylor, Charles; Blanco, Mario; Goddard, William

    2008-01-01

    A family of polymer/carbon films has been developed for use as sensory films in electronic noses for detecting SO2 gas at concentrations as low as 1 part per million (ppm). Most previously reported SO2 sensors cannot detect SO2 at concentrations below tens of ppm; only a few can detect SO2 at 1 ppm. Most of the sensory materials used in those sensors (especially inorganic ones that include solid oxide electrolytes, metal oxides, and cadmium sulfide) must be used under relatively harsh conditions that include operation and regeneration at temperatures greater than 100 C. In contrast, the present films can be used to detect 1 ppm of SO2 at typical opening temperatures between 28 and 32 C and can be regenerated at temperatures between 36 and 40 C. The basic concept of making sensing films from polymer/carbon composites is not new. The novelty of the present family of polymer/carbon composites lies in formulating the polymer components of these composites specifically to optimize their properties for detecting SO2. First-principles quantum-mechanical calculations of the energies of binding of SO2 molecules to various polymer functionalities are used as a guide for selecting polymers and understanding the role of polymer functionalities in sensing. The polymer used in the polymer-carbon composite is a copolymer of styrene derivative units with vinyl pyridine or substituted vinyl pyridine derivative units. To make a substituted vinyl pyridine for use in synthesizing such a polymer, poly(2-vinyl pyridine) that has been dissolved in methanol is reacted with 3-chloropropylamine that has been dissolved in a solution of methanol. The methanol is then removed to obtain the copolymer. Later, the copolymer can be dissolved in an appropriate solvent with a suspension of carbon black to obtain a mixture that can be cast and then dried to obtain a sensory film.

  2. Combinatorial Synthesis of and high-throughput protein release from polymer film and nanoparticle libraries.

    PubMed

    Petersen, Latrisha K; Chavez-Santoscoy, Ana V; Narasimhan, Balaji

    2012-09-06

    Polyanhydrides are a class of biomaterials with excellent biocompatibility and drug delivery capabilities. While they have been studied extensively with conventional one-sample-at-a-time synthesis techniques, a more recent high-throughput approach has been developed enabling the synthesis and testing of large libraries of polyanhydrides(1). This will facilitate more efficient optimization and design process of these biomaterials for drug and vaccine delivery applications. The method in this work describes the combinatorial synthesis of biodegradable polyanhydride film and nanoparticle libraries and the high-throughput detection of protein release from these libraries. In this robotically operated method (Figure 1), linear actuators and syringe pumps are controlled by LabVIEW, which enables a hands-free automated protocol, eliminating user error. Furthermore, this method enables the rapid fabrication of micro-scale polymer libraries, reducing the batch size while resulting in the creation of multivariant polymer systems. This combinatorial approach to polymer synthesis facilitates the synthesis of up to 15 different polymers in an equivalent amount of time it would take to synthesize one polymer conventionally. In addition, the combinatorial polymer library can be fabricated into blank or protein-loaded geometries including films or nanoparticles upon dissolution of the polymer library in a solvent and precipitation into a non-solvent (for nanoparticles) or by vacuum drying (for films). Upon loading a fluorochrome-conjugated protein into the polymer libraries, protein release kinetics can be assessed at high-throughput using a fluorescence-based detection method (Figures 2 and 3) as described previously(1). This combinatorial platform has been validated with conventional methods(2) and the polyanhydride film and nanoparticle libraries have been characterized with (1)H NMR and FTIR. The libraries have been screened for protein release kinetics, stability and

  3. Phase separation of polymer thin films and some applications

    NASA Astrophysics Data System (ADS)

    Zhu, Shaoming

    Phase separation of polymer thin film is a common issue in polymer thin film application. The existence of surface and surfactant are understood to play an important role in thin film final topography. In chapter two, the configuration of polymer blend thin film phase separation on cobalt substrate with PMMA phase forming column structure, and PS phase encapsulating the PMMA phase was used as resist mask to transfer the topographical feature to cobalt thin film. Isolated near spherical single and multi domain magnetic islands were obtained. The island made using this method had a broad single domain range from below 1000 to 5000A. In chapter three, when the polymer blend thin film was in bilayer configuration and diblock copolymer was added on the top layer, we found the confinement can increase the mixing of two homopolymers in highly incompatible polymer blends. By affecting the formation of micelles, the copolymers are forced to the interface between the two homopolymer phases where they reduce the interfacial tension to zero and form a microemulsion. Our findings have two important implications: first, they elucidate the role entropy plays in determining the phase behaviour of confined polymer blends and second, they offer a simple pathway to create thin film coatings with precisely controlled properties and surfaces. In chapter four, the kinetics process of microemulsion formation in confinement configuration has been analyzed. The microemulsion formation proceeded at initial stage by capillary wave, then it followed the growth regime t1/3 and lnt, then followed a more slow growth regime (lnt).56 or (lnt).60 till finally reached equilibrium, when the structure was frozen. In chapter five, we study the evolution of the morphologies of polymer blend thin films on silicon, cobalt, and gold substrates. In asymmetrical system, the substrate surface energy determined the wetting degree of the substrate preferring phases. In chapter six, we present a novel method for

  4. Fluorescent-conjugated polymer superquenching facilitates highly sensitive detection of proteases

    NASA Astrophysics Data System (ADS)

    Kumaraswamy, Sriram; Bergstedt, Troy; Shi, Xiaobo; Rininsland, Frauke; Kushon, Stuart; Xia, Wensheng; Ley, Kevin; Achyuthan, Komandoor; McBranch, Duncan; Whitten, David

    2004-05-01

    Sensor formats have been developed for detecting the activity of proteolytic enzymes based on fluorescent conjugated polymer superquenching. These sensors employ a reactive peptide sequence within a tether linking a quencher to a biotin. The peptide binds to sensors containing colocated biotin-binding protein and fluorescent polymer by means of biotin-biotin binding protein interactions, resulting in a strong quenching of polymer fluorescence. Enzyme-mediated cleavage of the peptide results in a reversal of the fluorescence quenching. These assays for protease activity are simple, sensitive, fast, and have the specificity required for screening chemical libraries for novel protease inhibitors in a high-throughput screening assay environment. These assays have been demonstrated for enterokinase, caspase-3/7, and -secretase.

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

    SciTech Connect

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

    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.

  6. The electrocaloric efficiency of ceramic and polymer films.

    PubMed

    Defay, Emmanuel; Crossley, Sam; Kar-Narayan, Sohini; Moya, Xavier; Mathur, Neil D

    2013-06-25

    Efficiency is defined as η = |Q|/|W| in order to investigate the electrical work |W| associated with electrocaloric heat |Q|. This materials parameter indicates that polymer films are slightly more energy efficient than ceramic films, and therefore both species of material remain candidates for future cooling applications.

  7. Phase equilibria in polymer blend thin films: a Hamiltonian approach.

    PubMed

    Souche, M; Clarke, N

    2009-12-28

    We propose a Hamiltonian formulation of the Flory-Huggins-de Gennes theory describing a polymer blend thin film. We then focus on the case of 50:50 polymer blends confined between antisymmetric walls. The different phases of the system and the transitions between them, including finite-size effects, are systematically studied through their relation with the geometry of the Hamiltonian flow in phase space. This method provides an easy and efficient way, with strong graphical insight, to infer the qualitative physical behavior of polymer blend thin films.

  8. Effect of CdSe nanoparticles on the fluorescence spectra of conjugate polymer P3HT: An experimental and theoretical study

    NASA Astrophysics Data System (ADS)

    Mastour, Nouha; Bouchriha, Habib

    2016-11-01

    In this work we have investigated the effect of CdSe nanoparticles (Nps) on the fluorescence spectra of conjugate polymer Poly(3-hexylthiophene-2,5-diyl) (P3HT). The fluorescence intensity is significantly decreased in both solution and solid films by the incorporation of CdSe Nps. This observed effect in the nanocomposite P3HT-CdSe is analyzed by using the Franck-Condon theory which reproduces correctly the decrease of the fluorescence with the Nps concentration and permits to reach the Huang-Rhys factor and the relaxation energy which are shown efficient to explain the fluorescence quenching.

  9. Film formation and mechanical behavior of polymer latexes

    SciTech Connect

    Gauthier, C.; Sindt, O.; Perez, J.

    1995-12-31

    The purpose of this lecture is to review the present state of the art in the field of film formation in relation with the mechanical behavior of polymer films. After a review of the theoretical approaches concerning film forming process, we show the influence of some experimental parameters (temperature, hygrometry {hor_ellipsis}) in the case of a core-shell latex obtained from polystyrene/Poly (Styrene co. butyl acrylate). Then, the mechanical behavior of polymer films is considered. The improvement of the mechanical strength of latex films during the last stage of film formation (i.e., gradual coalescence) is illustrated. Further analysis of the molecular process yielding mechanical behavior allows us to show how the comparison between prediction and experimental data can provide information on morphological changes, on the stability of this one, or on the formation of an interphase between constituting phases.

  10. Nanoscale control over phase separation in conjugated polymer blends using mesoporous silica spheres.

    PubMed

    Kelly, Timothy L; Yano, Kazuhisa; Wolf, Michael O

    2010-01-05

    A method of preparing blended conjugated polymer microparticles using mesoporous silica spheres is described. Poly(3,4-ethylenedioxythiophene) (PEDOT) was blended with poly(furfuryl alcohol) (PFA) by a sequential infiltration-polymerization approach. The materials were evaluated by both scanning and transmission electron microscopy and are shown to retain the overall spherical structure of the silica template. The filling of the mesopores and the polymer distribution within individual particles were determined by a combination of energy-dispersive X-ray microanalysis, X-ray photoelectron spectroscopy, and nitrogen adsorption. The results suggest that when PEDOT is added to the silica host, followed by PFA, the phase separation of the two immiscible polymers is constrained by the dimensions of the silica mesopores, ensuring nanoscale contact between the two phases. The silica template can be removed by etching with 25% hydrofluoric acid, leaving behind a blended polymer microparticle. The etched microparticles exhibit macroporous morphologies different from that of pure PEDOT particles prepared by a similar route. The blended microparticles also appear to undergo limited phase separation; no evidence for distinct polymer domains was observed. Conductivity measurements indicate that the blended particles are above the percolation threshold and support the conclusion that the phase domains are extremely small. Importantly, when PFA is added to the host first, followed by PEDOT, there is a striking difference to the final composition and morphology of the particles. This reversal of the blending order results in a more amorphous, phase-separated material. These results demonstrate the preparation of conjugated polymer blends with engineered nanoscale phase separation and may allow for future improvements in organic device architecture and performance.

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

    PubMed Central

    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

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

    NASA Astrophysics Data System (ADS)

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

    2015-05-01

    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.

  13. Drug-conjugated polymers as gene carriers for synergistic therapeutic effect.

    PubMed

    Pofali, P A; Singh, B; Dandekar, P; Jain, R D; Maharjan, S; Choi, Y J; Arote, R B; Cho, C S

    2016-05-01

    The ability to safely and effectively transfer gene into cells is the fundamental goal of gene delivery. In spite of the best efforts of researchers around the world, gene therapy has limited success. This may be because of several limitations of delivering gene which is one of the greatest technical challenges in the modern medicine. To address these issues, many efforts have been made to bind drugs and genes together by polymers for co-delivery to achieve synergistic effect. Usually, binding interaction of drugs with polymers is either physical or chemical. In case of drug-polymer physical interaction, the efficiency of drugs generally decreases because of separation of drugs from polymers in vivo whenever it comes in contact with charged biofluid/s or cells. While chemical interaction of drug-polymer overcomes the aforementioned obstacle, several problems such as steric hindrance, solubility, and biodegradability hinder it to develop as gene carrier. Considering these benefits and pitfalls, the objective of this review is to discuss the possible extent of drug-conjugated polymers as safe and efficient gene delivery carriers for achieving synergistic effect to combat various genetic disorders.

  14. Polymer fullerene solution phase behaviour and film formation pathways.

    PubMed

    Dattani, Rajeev; Cabral, João T

    2015-04-28

    We report the phase behaviour of polymer/fullerene/solvent ternary mixtures and its consequence for the morphology of the resulting composite thin films. We focus particularly on solutions of polystyrene (PS), C60 fullerene and toluene, which are examined by static and dynamic light scattering, and films obtained from various solution ages and thermal annealing conditions, using atomic force and light microscopy. Unexpectedly, the solution phase behaviour below the polymer overlap concentration, c*, is found to be described by a simple excluded volume argument (occupied by the polymer chains) and the neat C60/solvent miscibility. Scaling consistent with full exclusion is found when the miscibility of the fullerene in the solvent is much lower than that of the polymer, giving way to partial exclusion with more soluble fullerenes (phenyl-C61-butyric acid methyl ester, PCBM) and a less asymmetric solvent (chlorobenzene), employed in photovoltaic devices. Spun cast and drop cast films were prepared from PS/C60/toluene solutions across the phase diagram to yield an identical PS/C60 composition and film thickness, resulting in qualitatively different morphologies in agreement with our measured solution phase boundaries. Our findings are relevant to the solution processing of polymer/fullerene composites (including organic photovoltaic devices), which generally require effective solubilisation of fullerene derivatives and polymer pairs in this concentration range, and the design of well-defined thin film morphologies.

  15. Microporous polymer films and methods of their production

    DOEpatents

    Aubert, J.H.

    1995-06-06

    A process is described for producing thin microporous polymeric films for a variety of uses. The process utilizes a dense gas (liquefied gas or supercritical fluid) selected to combine with a solvent-containing polymeric film so that the solvent is dissolved in the dense gas, the polymer is substantially insoluble in the dense gas, and two phases are formed. A microporous film is obtained by removal of a dense gas-solvent phase. 9 figs.

  16. Microporous polymer films and methods of their production

    DOEpatents

    Aubert, James H.

    1995-01-01

    A process for producing thin microporous polymeric films for a variety of uses. The process utilizes a dense gas (liquified gas or supercritical fluid) selected to combine with a solvent-containing polymeric film so that the solvent is dissolved in the dense gas, the polymer is substantially insoluble in the dense gas, and two phases are formed. A microporous film is obtained by removal of a dense gas-solvent phase.

  17. Influence of film thickness on the phase separation mechanism in ultrathin conducting polymer blend films.

    PubMed

    Meier, Robert; Ruderer, Matthias A; Diethert, Alexander; Kaune, Gunar; Körstgens, Volker; Roth, Stephan V; Müller-Buschbaum, Peter

    2011-03-31

    The film morphology of thin polymer blend films based on poly[(1-methoxy)-4-(2-ethylhexyloxy)-p-phenylenevinylene] (MEH-PPV) and poly(N-vinylcarbazole) (PVK) is probed as a function of film thickness. Blend films are prepared with spin-coating of polymer solutions with different concentrations on top of solid supports. The blending ratio of both conducting polymers is kept constant. The film and surface morphology is probed with grazing incidence ultrasmall-angle X-ray scattering (GIUSAXS) and atomic force microscopy (AFM). A linear dependence between the film thickness and the averaged phase separation is found. In addition, X-ray reflectivity measurements show an enrichment of PVK at the substrate interface. UV/vis spectroscopy measurements indicate a linearly increasing amount of both homopolymers in the blend films for increasing film thicknesses. The generalized knowledge about the influence of the film thickness on the phase separation behavior in conducting polymer blend films is finally used to describe the phase separation formation during the spin-coating process, and the results are discussed in the framework of an adapted Flory-Huggins theory for rodlike polymers.

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

    PubMed

    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.

  19. Deviations from liquidlike behavior in molten polymer films at interfaces.

    PubMed

    Seo, Young-Soo; Koga, T; Sokolov, J; Rafailovich, M H; Tolan, M; Sinha, S

    2005-04-22

    We have performed x-ray specular and diffuse scattering on liquid polymer films and analyzed the spectra as a function of film thickness and molecular weight. The results show that films whose molecular weight is close to the entanglement length behave as simple liquids except that the shortest wavelength is determined by the radius of gyration (R(g)) rather than the monomer-monomer distance. When the molecular weight is higher than the entanglement length, the strong deviations from liquidlike behavior are observed. We find that the long wavelength cutoff vector, q(l,c), scales with film thickness, d as d(-1.1+/-0.1) rather than the usual d(-2) expected for simple liquids. If we assume that these deviations are due to surface pinning of the polymer chains, then our results are consistent with the formalism developed by Fredrickson et al. to explain the capillary wave spectrum that can propagate in a polymer brush.

  20. Directed Morphology of Nanofilled Polymer Films on Flexible Substrates

    NASA Astrophysics Data System (ADS)

    Bandyopadhyay, Diya; Hayirlioglu, Arzu; Kulkarni, Manish; Karim, Alamgir

    2011-03-01

    We demonstrate viable meso-patterning techniques that have relevance to electronics and organic photovoltaic applications via tunable control of polymer thin film instabilities. To this end, we examine the influence of fullerene (C60) nanoparticles on multicomponent polymer thin films on patterned and flexible polydimethylsiloxane substrates and compare these results to morphologies on hard silica xerogel substrates of variable roughness and surface energy. Controlled incorporation of nanoparticles (NPs) can be used to tune polymer thin film instabilities and morphology. At NP concentrations below a threshold value, we observe directed dewetting of blend thin films consisting of uniformly aligned dewet domains that mimic the periodicity of the confining media, consistent with our previous experiments where it was observed that C60 NPs preferentially segregate to a PS/PB blend interface up to a certain saturation concentration.

  1. Controlled release of tocopherols from polymer blend films

    NASA Astrophysics Data System (ADS)

    Obinata, Noe

    Controlled release packaging has great potential to increase storage stability of foods by releasing active compounds into foods continuously over time. However, a major limitation in development of this technology is the inability to control the release and provide rates useful for long term storage of foods. Better understanding of the factors affecting active compound release is needed to overcome this limitation. The objective of this research was to investigate the relationship between polymer composition, polymer processing method, polymer morphology, and release properties of active compounds, and to provide proof of principle that compound release is controlled by film morphology. A natural antioxidant, tocopherol was used as a model active compound because it is natural, effective, heat stable, and soluble in most packaging polymers. Polymer blend films were produced from combination of linear low density polyethylene (LLDPE) and high density polyethylene (HDPE), polypropylene (PP), or polystyrene (PS) with 3000 ppm mixed tocopherols using conventional blending method and innovative blending method, smart blending with a novel mixer using chaotic advection. Film morphologies were visualized with scanning electron microscopy (SEM). Release of tocopherols into 95% ethanol as a food simulant was measured by UV/Visible spectrophotometry or HPLC, and diffusivity of tocopherols in the polymers was estimated from this data. Polymer composition (blend proportions) and processing methods have major effects on film morphology. Four different types of morphologies, dispersed, co-continuous, fiber, and multilayer structures were developed by either conventional extrusion or smart blending. With smart blending of fixed polymer compositions, different morphologies were progressively developed with fixed polymer composition as the number of rod rotations increased, providing a way to separate effects of polymer composition and morphology. The different morphologies

  2. Light-Harvesting and Amplified Energy Transfer in Conjugated Polymer Nanoparticles.

    PubMed

    Jiang, Yifei; McNeill, Jason

    2017-01-25

    Conjugated polymer nanoparticles are a class of nanoparticles with many useful and interesting properties, including very high fluorescence brightness, excellent photostability, and sensing capabilities. They also exhibit interesting and potentially useful phenomena, such as highly efficient energy transfer, anomalous single particle blinking, and twinkling phenomena associated with polaron motion. As little as one dye molecule per nanoparticle can efficiently quench the fluorescence of hundreds of polymer chromophore units. Similarly, loss of a single electron can result in quenching of hundreds of chromophores. These phenomena and properties are dictated by the nature of interactions between chromophores in this dense, nanoscale multichromophoric system, and are characterized as amplified energy transfer or multiple energy transfer. In this review, we summarize the key aspects of conjugated polymer nanoparticles optical properties and phenomena, and discuss the current understanding of exciton dynamics in these and related systems. In particular, our current understanding and theoretical models for amplified or multiple energy transfer based on exciton theory and Förster resonance energy transfer are explored.

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

    PubMed

    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.

  4. Novel thiophene-bearing conjugated microporous polymer honeycomb-like porous spheres with ultrahigh iodine uptake.

    PubMed

    Ren, Feng; Zhu, Zhaoqi; Qian, Xin; Liang, Weidong; Mu, Peng; Sun, Hanxue; Liu, Jiehua; Li, An

    2016-07-28

    Two conjugated microporous polymers containing thiophene-moieties (SCMPs) were obtained by the polymerization of 3,3',5,5'-tetrabromo-2,2'-bithiophene and ethynylbenzene monomers through the palladium-catalyzed Sonogashira-Hagihara crosscoupling reaction. The resulting SCMPs show high thermal stability with a decomposition temperature above 300 °C. Scanning electron microscopy images show that the resulting SCMPs formed as an aggregation composed of micrometer-sized SCMP spheres, in which honeycomb-like porous spheres with penetrated pores on the surface were observed. Taking advantage of such a unique honeycomb-like porous morphology as well as π-conjugated structures, the SCMPs show ultrahigh absorption performance for iodine vapour with an uptake of up to 345 wt% obtained, which is the highest value reported to date for CMPs, thus making the resulting SCMPs ideal absorbent materials for reversible iodine capture to address environmental issues.

  5. Polymer-Chlorambucil Drug Conjugates: A Dynamic Platform of Anticancer Drug Delivery.

    PubMed

    Saha, Biswajit; Haldar, Ujjal; De, Priyadarsi

    2016-07-01

    Recently, polymer drug conjugates (PDCs) have attracted considerable attention in the treatment of cancer. In this work, a simple strategy has been developed to make PDCs of an antitumor alkylating agent, chlorambucil, using a biocompatible disulphide linker. Chlorambucil-based chain transfer agent was used to prepare various homopolymers and block copolymers in a controlled fashion via reversible addition-fragmentation chain transfer polymerization. Chlorambucil conjugated block copolymer, poly(polyethylene glycol monomethyl ether methacrylate)-b-poly(methyl methacrylate), formed nanoaggregates in aqueous solutions, which are characterized by dynamic light scattering and field emission-scanning electron microscopy. Finally, the simplicity of the design is exemplified by performing a release study of chlorambucil under reducing condition by using D,L-dithiothreitol.

  6. Vacuum deposited polymer/metal films for optical applications

    NASA Astrophysics Data System (ADS)

    Affinito, J. D.; Martin, P. M.; Gross, M. E.; Coronado, C.; Greenwell, E.

    1995-04-01

    Vacuum deposited Polymer/Silver/Polymer reflectors and Tantalum/Polymer/Aluminum Fabry-Perot interference filters were fabricated in a vacuun web coating operation on polyester substrates with a new, high speed deposition process. Reflectivities were measured in the wavelength range from 0.3 to 0.8(mu)m. This new vacuum processing technique has been shown to be capable of deposition line speeds in excess of 500 linear meters/minute. Central to this technique is a new position process for the high rate deposition of polymer films. This polymer process involves the flash evaporation of an acrylic monomer onto a moving substrate. The monomer is subsequently cured by an electron beam or ultraviolet light. This high speed polymer film deposition process has been named the PML process -- for Polymer Multi-Layer. Also, vacuum deposited, index matched, polymer/CaF(sub 2) composites were fabricated from monomer slurries that were subsequently cured with LTV light. This second technique is called the Liquid Multi-Layer (or LML) process. Each of these polymer processes is compatible with each other and with conventional vacuum deposition processes such as sputtering or evaporation.

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

    PubMed

    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.

  8. Numerical solutions of thin-film equations for polymer flows.

    PubMed

    Salez, Thomas; McGraw, Joshua D; Cormier, Sara L; Bäumchen, Oliver; Dalnoki-Veress, Kari; Raphaël, Elie

    2012-11-01

    We report on the numerical implementation of thin-film equations that describe the capillary-driven evolution of viscous films, in two-dimensional configurations. After recalling the general forms and features of these equations, we focus on two particular cases inspired by experiments: the leveling of a step at the free surface of a polymer film, and the leveling of a polymer droplet over an identical film. In each case, we first discuss the long-term self-similar regime reached by the numerical solution before comparing it to the experimental profile. The agreement between theory and experiment is excellent, thus providing a versatile probe for nanorheology of viscous liquids in thin-film geometries.

  9. Multilayered films fabricated from an oligoarginine-conjugated protein promote efficient surface-mediated protein transduction.

    PubMed

    Jewell, Christopher M; Fuchs, Stephen M; Flessner, Ryan M; Raines, Ronald T; Lynn, David M

    2007-03-01

    The conjugation of cationic protein transduction domains to proteins results in an increase in the extent to which proteins are internalized by cells. This investigation sought to determine whether the conjugation of a protein transduction domain to a functional protein could be used to facilitate the incorporation of the protein into multilayered polyelectrolyte films and, subsequently, whether these films could be used to promote surface-mediated protein transduction. We demonstrate that it is possible to fabricate multilayered assemblies 80 nm thick using sodium polystyrene sulfonate (SPS) and bovine pancreatic ribonuclease (RNase A) conjugated to the cationic protein transduction domain nonaarginine (R(9)) using an entirely aqueous layer-by-layer process. We demonstrate further that the conjugation of R(9) to RNase A permits the assembly of multilayered films under conditions that do not allow for the incorporation of the unmodified protein. This result suggests that R(9) functions as a cationic anchor and serves to increase the strength of electrostatic interactions with SPS and facilitate layer-by-layer assembly. We also demonstrate that RNase A-R(9)/SPS films dissolve rapidly in physiologically relevant media and that macroscopic objects coated with these materials can be used to mediate high levels of protein transduction in mammalian cells. These results suggest the basis of general methods that could contribute to the design of materials that permit spatial and temporal control over the delivery of therapeutic proteins to cells and tissues.

  10. The Evolution of Thin-Film Structure in pi-Conjugated System: Implications for Devices

    DTIC Science & Technology

    2015-07-09

    AFRL-OSR-VA-TR-2015-0157 The Evolution of Thin-Film Structure in pi-Conjugated System Elsa Reichmanis GEORGIA TECH RESEARCH CORPORATION Final Report...NUMBER 5e.  TASK NUMBER 5f.  WORK UNIT NUMBER 7.  PERFORMING ORGANIZATION NAME(S) AND ADDRESS(ES) GEORGIA TECH RESEARCH CORPORATION 505 10TH ST NW

  11. Simulated Space Vacuum Ultraviolet (VUV) Exposure Testing for Polymer Films

    NASA Technical Reports Server (NTRS)

    Dever, Joyce A.; Pietromica, Anthony J.; Stueber, Thomas J.; Sechkar, Edward A.; Messer, Russell K.

    2002-01-01

    Vacuum ultraviolet (VUV) radiation of wavelengths between 115 and 200 nm produced by the sun in the space environment can cause degradation to polymer films producing changes in optical, mechanical, and chemical properties. These effects are particularly important for thin polymer films being considered for ultra-lightweight space structures, because, for most polymers, VUV radiation is absorbed in a thin surface layer. NASA Glenn Research Center has developed facilities and methods for long-term ground testing of polymer films to evaluate space environmental VUV radiation effects. VUV exposure can also be used as part of sequential simulated space environmental exposures to determine combined damaging effects. This paper will describe the effects of VUV on polymer films and the necessity for ground testing. Testing practices used at Glenn Research Center for VUV exposure testing will be described including characterization of the VUV radiation source used, calibration procedures traceable to the National Institute of Standards and Technology (NIST), and testing techniques for VUV exposure of polymer surfaces.

  12. Patterning Multicomponent Polymer Thin Films via Dynamic Thermal Processing

    NASA Astrophysics Data System (ADS)

    Singh, Gurpreet

    Bottom-up patterning is gaining increased importance owing to the physical limitations and rising costs of top-down patterning. One example of bottom-up patterning is self-assembling polymer thin films. Although there are several pathways to facilitate polymer thin film self-assembly, this presentation will focus on dynamic thermal field based processes for patterning multicomponent polymer thin films. Dynamic thermal field processing is an attractive roll­to­roll (R2R) amenable directed self­assembly (DSA) method for molecular level organization of multicomponent polymer systems such as block copolymer thin films over large areas without requiring guiding templates. The talk will first outline how parameters such as magnitude of the temperature gradient, velocity of annealing, thermal expansion, and molecular weight of the polymer can be optimized to finely tune the morphology of the block copolymer thin films and also elucidate their associated physical mechanisms. The second part of the talk will outline application of dynamic thermal field processes for fabricating functional nanomaterials and discuss the recent advancements achieved using these processes.

  13. Lattice cluster theory for dense, thin polymer films.

    PubMed

    Freed, Karl F

    2015-04-07

    While the application of the lattice cluster theory (LCT) to study the miscibility of polymer blends has greatly expanded our understanding of the monomer scale molecular details influencing miscibility, the corresponding theory for inhomogeneous systems has not yet emerged because of considerable technical difficulties and much greater complexity. Here, we present a general formulation enabling the extension of the LCT to describe the thermodynamic properties of dense, thin polymer films using a high dimension, high temperature expansion. Whereas the leading order of the LCT for bulk polymer systems is essentially simple Flory-Huggins theory, the highly non-trivial leading order inhomogeneous LCT (ILCT) for a film with L layers already involves the numerical solution of 3(L - 1) coupled, highly nonlinear equations for the various density profiles in the film. The new theory incorporates the essential "transport" constraints of Helfand and focuses on the strict imposition of excluded volume constraints, appropriate to dense polymer systems, rather than the maintenance of chain connectivity as appropriate for lower densities and as implemented in self-consistent theories of polymer adsorption at interfaces. The ILCT is illustrated by presenting examples of the computed profiles of the density, the parallel and perpendicular bonds, and the chain ends for free standing and supported films as a function of average film density, chain length, temperature, interaction with support, and chain stiffness. The results generally agree with expected general trends.

  14. Lattice cluster theory for dense, thin polymer films

    SciTech Connect

    Freed, Karl F.

    2015-04-07

    While the application of the lattice cluster theory (LCT) to study the miscibility of polymer blends has greatly expanded our understanding of the monomer scale molecular details influencing miscibility, the corresponding theory for inhomogeneous systems has not yet emerged because of considerable technical difficulties and much greater complexity. Here, we present a general formulation enabling the extension of the LCT to describe the thermodynamic properties of dense, thin polymer films using a high dimension, high temperature expansion. Whereas the leading order of the LCT for bulk polymer systems is essentially simple Flory-Huggins theory, the highly non-trivial leading order inhomogeneous LCT (ILCT) for a film with L layers already involves the numerical solution of 3(L − 1) coupled, highly nonlinear equations for the various density profiles in the film. The new theory incorporates the essential “transport” constraints of Helfand and focuses on the strict imposition of excluded volume constraints, appropriate to dense polymer systems, rather than the maintenance of chain connectivity as appropriate for lower densities and as implemented in self-consistent theories of polymer adsorption at interfaces. The ILCT is illustrated by presenting examples of the computed profiles of the density, the parallel and perpendicular bonds, and the chain ends for free standing and supported films as a function of average film density, chain length, temperature, interaction with support, and chain stiffness. The results generally agree with expected general trends.

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

    PubMed

    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.

  16. Dielectric breakdown in silica-amorphous polymer nanocomposite films: the role of the polymer matrix.

    PubMed

    Grabowski, Christopher A; Fillery, Scott P; Westing, Nicholas M; Chi, Changzai; Meth, Jeffrey S; Durstock, Michael F; Vaia, Richard A

    2013-06-26

    The ultimate energy storage performance of an electrostatic capacitor is determined by the dielectric characteristics of the material separating its conductive electrodes. Polymers are commonly employed due to their processability and high breakdown strength; however, demands for higher energy storage have encouraged investigations of ceramic-polymer composites. Maintaining dielectric strength, and thus minimizing flaw size and heterogeneities, has focused development toward nanocomposite (NC) films; but results lack consistency, potentially due to variations in polymer purity, nanoparticle surface treatments, nanoparticle size, and film morphology. To experimentally establish the dominant factors in broad structure-performance relationships, we compare the dielectric properties for four high-purity amorphous polymer films (polymethyl methacrylate, polystyrene, polyimide, and poly-4-vinylpyridine) incorporating uniformly dispersed silica colloids (up to 45% v/v). Factors known to contribute to premature breakdown-field exclusion and agglomeration-have been mitigated in this experiment to focus on what impact the polymer and polymer-nanoparticle interactions have on breakdown. Our findings indicate that adding colloidal silica to higher breakdown strength amorphous polymers (polymethyl methacrylate and polyimide) causes a reduction in dielectric strength as compared to the neat polymer. Alternatively, low breakdown strength amorphous polymers (poly-4-vinylpyridine and especially polystyrene) with comparable silica dispersion show similar or even improved breakdown strength for 7.5-15% v/v silica. At ∼15% v/v or greater silica content, all the polymer NC films exhibit breakdown at similar electric fields, implying that at these loadings failure becomes independent of polymer matrix and is dominated by silica.

  17. Pattern formation and evolution in thin polymer films

    NASA Astrophysics Data System (ADS)

    Masson, Jean-Loup Didier

    2001-07-01

    Thin polymer films are important for many technologies. They are used as coatings, adhesives, lubricants and for device technologies, such as polymer based light-emitting diodes. Several concerns arise when processing and using thin polymer films. Properties of thin polymer films (e.g., viscosity, diffusion, glass transition temperature) are different from bulk properties due to finite size effects (e.g., confinement of the chains) and to interfacial interactions (e.g., presence of the free surface and the substrate). Moreover, the stability of the film on the substrate is of concern. Thin polymer films, of thickness h < 100 nm, fabricated on a substrate may rupture under destabilizing forces, such as van der Waals forces. Rupturing exposes the underlying substrate and the exposed regions will grow, provided that the spreading coefficient is negative. This process is known as dewetting. Thus far, two dewetting morphologies have been identified but little is understood about their formation and evolution. The first morphology consists of circular holes throughout the film and the second morphology is reminiscent of patterns associated with spinodal decomposition processes. In this research, we investigated four problems. First, we examined fundamental questions related to the formation and evolution of patterns on the substrate. We documented the existence of different dynamic stages of evolution associated with different driving forces for both "conventional" morphologies (circular holes and "spinodal-like"). Second, we discovered a new morphology that occurs in a thin random copolymer film on a silicon substrate. This morphology results from heterogeneous interactions of the chain segments with the substrate. Third, we examined flow processes in thin polymer films (chain dynamics near surfaces). We show that a fingering instability develop spontaneously at the moving liquid front when the film is below a critical thickness that depends on the length of the chains

  18. Functionalization of boron diiminates with unique optical properties: multicolor tuning of crystallization-induced emission and introduction into the main chain of conjugated polymers.

    PubMed

    Yoshii, Ryousuke; Hirose, Amane; Tanaka, Kazuo; Chujo, Yoshiki

    2014-12-31

    In this article, we report the unique optical characteristics of boron diiminates in the solid states. We synthesized the boron diiminates exhibiting aggregation-induced emission (AIE). From the series of optical measurements, it was revealed that the optical properties in the solid state should be originated from the suppression of the molecular motions of the boron diiminate units. The emission colors were modulated by the substitution effects (λ(PL,crystal) = 448-602 nm, λ(PL,amorphous) = 478-645 nm). Strong phosphorescence was observed from some boron diiminates deriving from the effects of two imine groups. Notably, we found some of boron diiminates showed crystallization-induced emission (CIE) properties derived from the packing differences from crystalline to amorphous states. The 15-fold emission enhancement was observed by the crystallization (Φ(PL,crystal) = 0.59, Φ(PL,amorphous) = 0.04). Next, we conjugated boron diiminates with fluorene. The synthesized polymers showed good solubility in the common solvents, film formability, and thermal stability. In addition, because of the expansion of main-chain conjugation, the peak shifts to longer wavelength regions were observed in the absorption/emission spectra of the polymers comparing to those of the corresponding boron diiminate monomers (λ(abs) = 374-407 nm, λ(PL) = 509-628 nm). Furthermore, the absorption and the emission intensities were enhanced via the light-harvesting effect by the conjugation with fluorene. Finally, we also demonstrated the dynamic reversible alterations of the optical properties of the polymer thin films by exposing to acidic or basic vapors.

  19. Influence of substrate and film thickness on polymer LIPSS formation

    NASA Astrophysics Data System (ADS)

    Cui, Jing; Nogales, Aurora; Ezquerra, Tiberio A.; Rebollar, Esther

    2017-02-01

    Here we focus on the influence of both, substrate and film thickness on polymer Laser Induced Periodic Surface Structures (LIPSS) formation in polymer films. For this aim a morphological description of ripples structures generated on spin-coated polystyrene (PS) films by a linearly polarized laser beam with a wavelength of 266 nm is presented. The influence of different parameters on the quality and characteristics of the formed laser-induced periodic surface structures (LIPSS) was investigated. We found that well-ordered LIPSS are formed either on PS films thinner than 200 nm or thicker than 400 nm supported on silicon substrates as well as on thicker free standing films. However less-ordered ripples are formed on silicon supported films with intermediate thicknesses in the range of 200-380 nm. The effect of the thermal and optical properties of the substrate on the quality of LIPSS was analyzed. Differences observed in the fluence and number of pulses needed for the onset of surface morphological modifications is explained considering two main effects which are: (1) The temperature increase on polymer surface induced by the action of cumulative laser irradiation and (2) The differences in thermal conductivity between the polymer and the substrate which strongly affect the heat dissipation generated by irradiation.

  20. Electrochemical considerations for determining absolute frontier orbital energy levels of conjugated polymers for solar cell applications.

    PubMed

    Cardona, Claudia M; Li, Wei; Kaifer, Angel E; Stockdale, David; Bazan, Guillermo C

    2011-05-24

    Narrow bandgap conjugated polymers in combination with fullerene acceptors are under intense investigation in the field of organic photovoltaics (OPVs). The open circuit voltage, and thereby the power conversion efficiency, of the devices is related to the offset of the frontier orbital energy levels of the donor and acceptor components, which are widely determined by cyclic voltammetry. Inconsistencies have appeared in the use of the ferrocenium/ferrocene (Fc + /Fc) redox couple, as well as the values used for the absolute potentials of standard electrodes, which can complicate the comparison of materials properties and determination of structure/property relationships.

  1. One-step nanopatterning of conjugated polymers by electron-beam-assisted electropolymerization

    PubMed Central

    Higuchi, Takeshi; Nishiyama, Hidetoshi; Suga, Mitsuo; Watanabe, Hirohmi; Takahara, Atsushi; Jinnai, Hiroshi

    2015-01-01

    We propose a one-step nanopatterning method where liquid monomers are polymerized directly with an electron beam under an atmospheric pressure. The method allows precise positional control of an electron beam that induces electropolymerization based on an anodic oxidation only in the irradiated areas. Various versatile conjugated polymers, including polypyrrole, polyaniline and poly(3-hexylthiophene), have been directly polymerized from monomers without solvents and patterned by our one-step nanopatterning method. Vertically oriented arrays of nanorods several hundred nanometers in diameter with an aspect ratio (height to diameter) of around two were fabricated. PMID:25825510

  2. Enhanced photooxidative stability of conjugated polymers via C{sub 60} doping

    SciTech Connect

    Sarkas, H.W.; Kwan, W.; Flom, S.R.; Merritt, C.D.; Kafafi, Z.H.

    1996-03-28

    The effect of C{sub 60} doping on the photooxidative stability of the conjugated polymer poly[2-methoxy-5-(2`-ethylhexyloxy)-p-phenylene vinylene] (MEH-PPV) is investigated via Fourier transform infrared and ultraviolet-visible absorption spectroscopies. The photooxidation of both MEH-PPV and MEH-PPV/C{sub 60} exhibits first-order kinetics. Analysis reveals that C{sub 60} slows the rate of photodegradation of MEH-PPV by more than an order of magnitude. 22 refs., 4 figs.

  3. Conjugated-polymer-based energy-transfer systems for antimicrobial and anticancer applications.

    PubMed

    Yuan, Huanxiang; Wang, Bing; Lv, Fengting; Liu, Libing; Wang, Shu

    2014-10-29

    Conjugated polymers (CPs) attract a lot of attention in sensing, imaging, and biomedical applications because of recent achievements that are highlighted in this Research News article. A brief review of recent progress in the application of CP-based energy-transfer systems in antimicrobial and anticancer treatments is provided. The transfer of excitation energy from CPs to photosensitizers leads to the generation of reactive oxygen species (ROS) that are able to efficiently kill pathogenic microorganisms and cancer cells in the surroundings. Both fluorescence resonance energy transfer (FRET) and bioluminescence energy transfer (BRET) modes are discussed.

  4. Fluorescence quenching of water-soluble conjugated polymer by metal cations and its application in sensor.

    PubMed

    Chen, Yan-Guo; Zhao, Dan; He, Zhi-Ke; Ai, Xin-Ping

    2007-02-01

    The effects of different metal cations on the fluorescence of water-soluble conjugated polymer (CP) and their quenching mechanism have been explored. Most transition metal cations, especially noble metal cations, such as Pd2+, Ru3+, and Pt2+ possessed higher quenching efficiency to CP fluorescence than that of the main group metal cations and other transition metal cations, which have filled or half-full outmost electron layer configurations. Base on this, rapid, sensitive detection of noble metal cations can be realized and a novel quencher-tether-ligand (QTL) probe was developed to detect avidin and streptavidin.

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

    PubMed

    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.

  6. Use of steric encumbrance to develop conjugated nanoporous polymers for metal-free catalytic hydrogenation

    SciTech Connect

    Tian, Chengcheng; Zhu, Xiang; Abney, Carter W.; Tian, Ziqi; Jiang, De-en; Han, Kee Sung; Mahurin, Shannon M.; Washton, Nancy M.; Dai, Sheng

    2016-01-01

    The design and synthesis of metal-free heterogeneous catalysts for efficient hydrogenation remains a great challenge. Here we report a novel approach to create conjugated nanoporous polymers with efficient hydrogenation activities toward unsaturated ketones by leveraging the innate steric encumbrance. The steric bulk of the framework as well as the local sterics of the Lewis basic sites within the polymeric skeleton result in the generation of the putative catalyst. This approach opens up new possibilities for the development of innovative metal-free heterogeneous catalysts.

  7. Detecting Airborne Mercury by Use of Polymer/Carbon Films

    NASA Technical Reports Server (NTRS)

    Shevade, Abhijit; Ryan, Margaret; Homer, Margie; Kisor, Adam; Jewell, April; Yen, Shiao-Pin; Manatt, Kenneth; Blanco, Mario; Goddard, William

    2009-01-01

    Films made of certain polymer/carbon composites have been found to be potentially useful as sensing films for detecting airborne elemental mercury at concentrations on the order of tens of parts per billion or more. That is to say, when the polymer/carbon composite films are exposed to air containing mercury vapor, their electrical resistances decrease by measurable amounts. Because airborne mercury is a health hazard, it is desirable to detect it with great sensitivity, especially in enclosed environments in which there is a risk of a mercury leak from lamps or other equipment. The present effort to develop polymerbased mercury-vapor sensors complements the work reported in NASA Tech Briefs Detecting Airborne Mercury by Use of Palladium Chloride (NPO- 44955), Vol. 33, No. 7 (July 2009), page 48 and De tecting Airborne Mer cury by Use of Gold Nanowires (NPO-44787), Vol. 33, No. 7 (July 2009), page 49. Like those previously reported efforts, the present effort is motivated partly by a need to enable operation and/or regeneration of sensors under relatively mild conditions more specifically, at temperatures closer to room temperature than to the elevated temperatures (greater than 100 C ) needed for regeneration of sensors based on noble-metal films. The present polymer/carbon films are made from two polymers, denoted EYN1 and EYN2 (see Figure 1), both of which are derivatives of poly-4-vinyl pyridine with amine functional groups. Composites of these polymers with 10 to 15 weight percent of carbon were prepared and solution-deposited onto the JPL ElectronicNose sensor substrates for testing. Preliminary test results showed that the resulting sensor films gave measurable indications of airborne mercury at concentrations on the order of tens of parts per billion (ppb) or more. The operating temperature range for the sensing films was 28 to 40 C and that the sensor films regenerated spontaneously, without heating above operating temperature (see Figure 2).

  8. Optically induced mode splitting in self-assembled, high quality-factor conjugated polymer microcavities

    PubMed Central

    Braam, Daniel; Kushida, Soh; Niemöller, Robert; Prinz, Günther M.; Saito, Hitoshi; Kanbara, Takaki; Kuwabara, Junpei; Yamamoto, Yohei; Lorke, Axel

    2016-01-01

    We investigate the whispering gallery modes (WGMs) of self-assembled single microspheres. They consist of a recently developed highly fluorescent π-conjugated copolymer and exhibit excellent optical properties with Q-factors up to 104. Under continuous laser irradiation, we observe a splitting of the highly degenerate spherical WGMs into a multiplet of lines. Comparison with the calculated spectral response of a weakly distorted sphere shows that the optical excitation induces a change of the optical path length in the microcavity so that it resembles a prolate spheroid. The separation of the lines is given by the ellipticity and the azimuthal mode number. Measurements in various gaseous environments suggest that the distortion is caused by light induced oxidation of the polymer. Our findings show that photooxidation can be a beneficial mechanism for in-situ tuning of optically active polymer structures. PMID:26781838

  9. Solvent-modified ultrafast decay dynamics in conjugated polymer/dye labeled single stranded DNA

    NASA Astrophysics Data System (ADS)

    Kim, Inhong; Kang, Mijeong; Woo, Han Young; Oh, Jin-Woo; Kyhm, Kwangseuk

    2015-07-01

    We have investigated that organic solvent (DMSO, dimethyl sulfoxide) modifies energy transfer efficiency between conjugated polymers (donors) and fluorescein-labeled single stranded DNAs (acceptors). In a mixture of buffer and organic solvent, fluorescence of the acceptors is significantly enhanced compared to that of pure water solution. This result can be attributed to change of the donor-acceptor environment such as decreased hydrophobicity of polymers, screening effect of organic solvent molecules, resulting in an enhanced energy transfer efficiency. Time-resolved fluorescence decay of the donors and the acceptors was modelled by considering the competition between the energy harvesting Foerster resonance energy transfer and the energy-wasting quenching. This enables to quantity that the Foerster distance (R0 = 43.3 Å) and resonance energy transfer efficiency (EFRET = 58.7 %) of pure buffer solution become R0 = 38.6 Å and EFRET = 48.0 % when 80% DMSO/buffer mixture is added.

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

    NASA Astrophysics Data System (ADS)

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

    2014-07-01

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

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

    NASA Astrophysics Data System (ADS)

    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).

  12. Unraveling the Electronic Heterogeneity of Charge Traps in Conjugated Polymers by Single-Molecule Spectroscopy.

    PubMed

    Adachi, Takuji; Vogelsang, Jan; Lupton, John M

    2014-02-06

    Charge trapping is taken for granted in modeling the characteristics of organic semiconductor devices, but very few techniques actually exist to spectroscopically pinpoint trap states. For example, trap levels are often assumed to be discrete in energy. Using the well-known keto defect in polyfluorene as a model, we demonstrate how single-molecule spectroscopy can directly track the formation of charge and exciton traps in conjugated polymers in real time, providing crucial information on the energetic distribution of trap sites relative to the polymer optical gap. Charge traps with universal spectral fingerprints scatter by almost 1 eV in depth, implying that substantial heterogeneity must be taken into account when modeling devices.

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

    PubMed

    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.

  14. Dry-film polymer waveguide for silicon photonics chip packaging.

    PubMed

    Hsu, Hsiang-Han; Nakagawa, Shigeru

    2014-09-22

    Polymer waveguide made by dry film process is demonstrated for silicon photonics chip packaging. With 8 μm × 11.5 μm core waveguide, little penalty is observed up to 25 Gbps before or after the light propagate through a 10-km long single-mode fiber (SMF). Coupling loss to SMF is 0.24 dB and 1.31 dB at the polymer waveguide input and output ends, respectively. Alignment tolerance for 0.5 dB loss increase is +/- 1.0 μm along both vertical and horizontal directions for the coupling from the polymer waveguide to SMF. The dry-film polymer waveguide demonstrates promising performance for silicon photonics chip packaging used in next generation optical multi-chip module.

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

    PubMed

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

    2013-07-25

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

  16. Spinodal Clustering in Thin Films of Nanoparticle-Polymer Mixtures

    NASA Astrophysics Data System (ADS)

    Wong, Him Cheng; Cabral, João T.

    2010-07-01

    Thin supported polystyrene-C60 fullerene mixtures annealed above their glass transition temperature develop spinodal surface undulations which depend on film thickness h(20-500nm), polymer molecular mass Mw, temperature, and time t. The dominant wavelength λ˜1-10μm scales linearly with h and coarsening kinetics follow λ˜tα, with 0<α(h)<1/3; the morphology eventually pins at long times. This spinodal surface excitation contrasts with dewetting suppression and film stability observed in low-Mw polymers and results from the interplay of binary miscibility and fullerene substrate attraction.

  17. Nanostructure investigation of polymer solutions, polymer gels, and polymer thin films

    NASA Astrophysics Data System (ADS)

    Lee, Wonjoo

    This thesis discusses two systems. One is structured hydrogels which are hydrogel systems based on crosslinked poly((2-dimethylamino)ethyl methacrylate) (PDMAEMA) containing micelles which form nanoscale pores within the PDMAEMA hydrogel. The other is nanoporous block copolymer thin films where solvent selectivity is exploited to create nanopores in PS-b-P4VP thin films. Both of these are multicomponent polymer systems which have nanoscale porous structures. 1. Small angle neutron scattering of micellization of anionic surfactants in water, polymer solutions and hydrogels. Nanoporous materials have been broadly investigated due to the potential for a wide range of applications, including nano-reactors, low-K materials, and membranes. Among those, molecularly imprinted polymers (MIP) have attracted a large amount of interest because these materials resemble the "lock and key" paradigm of enzymes. MIPs are created by crosslinking either polymers or monomers in the presence of template molecules, usually in water. Initially, functional groups on the polymer or the monomer are bound either covalently or noncovalently to the template, and crosslinking results in a highly crosslinked hydrogel. The MIPs containing templates are immersed in a solvent (usually water), and the large difference in the osmotic pressure between the hydrogel and solvent removes the template molecules from the MIP, leaving pores in the polymer network containing functionalized groups. A broad range of different templates have been used ranging from molecules to nanoscale structures inclucing stereoisomers, virus, and micelles. When micelles are used as templates, the size and shape before and after crosslinking is an important variable as micelles are thermodynamic objects whose structure depends on the surfactant concentration of the solution, temperature, electrolyte concentration and polymer concentration. In our research, the first goal is to understand the micellization of anionic

  18. Long Circulating Micelles based on Helix Bundle-Forming Peptide-Polymer Conjugates

    NASA Astrophysics Data System (ADS)

    Shu, Jessica; Dong, He; Dube, Nikhil; Seo, Jai Woong; Ma, Yu Fei; Ferrara, Katherine; Xu, Ting

    2012-02-01

    Stable, multi-functional organic nanoparticles that combine long in vivo circulation, the ability to cross vessel walls to reach tumor tissues and controlled disassembly for eventual clearance will have a significant impact in nanomedicine. Although current self-assemblies of amphiphiles provide a versatile platform to generate modular organic nanoparticles, it remains a significant challenge to simultaneously control nanoparticle size in the range of 10-30 nm, enhance particle stability and tailor disassembly within suitable timescales. We have advanced this goal by designing a new family of amphiphiles based on coiled-coil 3-helix bundle forming peptide-polymer conjugates. By attaching a polymer chain to the middle of a helical peptide, the protein tertiary structures are used to position entropic forces of compressed polymer chains comprising the headgroups so as to effectively slow down the subunit desorption rate and enhance the in vivo stability. The resultant monodispersed nanoparticles are composed of subunits, < 4 nm in size, that form highly stable 15-17 nm diameter particles and demonstrate an in vivo circulation half life-time of 28 hrs, minimal accumulation in the liver and spleen and effective urinary clearance. By uniquely combining the configurational entropy of a polymer chain with a common protein structure, i.e. coiled-coil helix bundle, and a lipid core, self-assembled nanoparticles have been engineered with tunable stability and disassembly.

  19. Conjugated Polymer Blend Microspheres for Efficient, Long-Range Light Energy Transfer.

    PubMed

    Kushida, Soh; Braam, Daniel; Dao, Thang Duy; Saito, Hitoshi; Shibasaki, Kosuke; Ishii, Satoshi; Nagao, Tadaaki; Saeki, Akinori; Kuwabara, Junpei; Kanbara, Takaki; Kijima, Masashi; Lorke, Axel; Yamamoto, Yohei

    2016-05-24

    Highly luminescent π-conjugated polymeric microspheres were fabricated through self-assembly of energy-donating and energy-accepting polymers and their blends. To avoid macroscopic phase separation, the nucleation time and growth rate of each polymer in the solution were properly adjusted. Photoluminescence (PL) studies showed that efficient donor-to-acceptor energy transfer takes place inside the microspheres, revealing that two polymers are well-blended in the microspheres. Focused laser irradiation of a single microsphere excites whispering gallery modes (WGMs), where PL generated inside the sphere is confined and resonates. The wavelengths of the PL lines are finely tuned by changing the blending ratio, accompanying the systematic yellow-to-red color change. Furthermore, when several microspheres are coupled linearly, the confined PL propagates the microspheres through the contact point, and a cascade-like process converts the PL color while maintaining the WGM characteristics. The self-assembly strategy for the formation of polymeric nano- to microstructures with highly miscible polymer blends will be advantageous for optoelectronic and photonic device applications.

  20. Reversible thermochromic polymer film embedded with fluorescent organogel nanofibers.

    PubMed

    Kim, Hyungwoo; Chang, Ji Young

    2014-11-18

    We report a reversible thermochromic nanocomposite polymer film composed of fluorescent organogel fibers and a highly cross-linked polymer matrix. A series of cyano-substituted oligo(p-phenylenevinylene) (CN-OPV) derivatives were synthesized by the reaction of dialdehydes with phenyl or naphthyl acetonitrile under basic conditions. Among the CN-OPV derivatives, NA-DBA having naphtyl moieties and dodecyloxy chains formed a stable organogel in a cross-linkable monomeric solvent (ethylene glycol dimethacrylate). The organogel showed a thermoreversible sol-gel transition, accompanying the emission color change. A nanocomposite polymer film obtained by photopolymerization of the organogel between two quartz plates also exhibited reversible thermochromism. Under 365 nm irradiation, the orange color of the film at 25 °C became yellowish green at 120 °C. The fluorescence spectroscopy, DSC, and microscopy results determined that the thermally reversible self-assembly of NA-DBA occurred in the polymer matrix, resulting in reversible thermochromism. The melted gelator molecules at 120 °C did not diffuse into the polymer matrix probably because of poor interactions of the gelator molecules with the polymer matrix. The NA-DBA molecules dispersed in poly(methyl methacrylate), without forming a supramolecular structure, did not show thermochromism.

  1. Characterization of solution structure and its importance in thin film ordering of conjugated block copolymers for organic semiconductor devices

    NASA Astrophysics Data System (ADS)

    Brady, Michael; Ku, Sung-Yu; Cochran, Justin; Wang, Cheng; Hawker, Craig; Kramer, Edward; Chabinyc, Michael

    2014-03-01

    Fully conjugated diblock copolymers (CBCPs) form intriguing materials alternatives to polymer-small molecule blends for their control of mesoscopic order in low-cost organic semiconductor devices. In both bulk heterojunction (BHJ) photovoltaics, consisting of an interpenetrating network with high donor-acceptor interfacial area, and ambipolar transistors, the transport of charge carriers through continuous p- and n-type paths in thin films is a controlling factor in device performance. AFM, GIWAXS, NEXAFS spectroscopy, and RSoXS are used to probe the structure of films of CBCPs with a p-type P3HT block and an n-type DPP block. Thermal annealing in the P3HT melt after casting creates ordered domains with ~ 50 nm in-plane lamellar spacings, as confirmed with GISAXS and RSoXS. GIWAXS diffraction from the (h00) alkyl-stacking and (010) pi-stacking planes shows primarily edge-on orientation for crystals of both P3HT and DPP blocks. In addition, temperature-dependent solution SAXS and UV-Vis spectroscopy are used to probe the size and conformation of casting solution aggregates. Fibrillar DPP aggregates direct the crystallization of P3HT- b-DPP following film casting and enable the formation of wormlike domains after annealing and thus ideal morphologies for transport in organic devices.

  2. Probing nano-rheology in thin polymer films

    NASA Astrophysics Data System (ADS)

    Dalnoki-Veress, Kari

    2013-03-01

    In this talk I will summarize our recent work on using stepped films to uncover some of the physics relevant to polymer rheology on length scales comparable to the size of polymer molecules. The work presented will focus on the efforts of a larger collaboration (Elie Raphael's theory group in Paris and James Forrest's group in Waterloo). The simple geometry of a polymer film on a substrate with a step at the free surface is unfavourable due to the excess interface induced by the step. Laplace pressure will drive flow within the film which can be studied with optical and atomic force microscopies. Because of the excellent agreement between theory and experiment when we probe ``bulk-like'' properties, these studies provide an opportunity to study how such systems transition from the bulk to confined. Starting with some of the results of levelling experiments on simple stepped films as well as the levelling of polymer droplets on thin films, I will finish with a discussion on our more recent efforts to elucidate confinement effects.

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

    NASA Astrophysics Data System (ADS)

    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.

  4. Selective crystallization of conjugated polymers into nanowires from graphene coated surfaces

    NASA Astrophysics Data System (ADS)

    Acevedo-Cartagena, Daniel; Zhu, Jiaxin; Trabanino, Elvira; Pentzer, Emily; Emrick, Todd; Briseño, Alejandro; Nonnenmann, Stephen; Hayward, Ryan

    Solution-based crystallization of conjugated polymers offers a scalable and attractive route to develop hierarchical structures for organic electronic devices, especially solar cells. The introduction of well-defined nucleation sites into metastable supersaturated solutions provides a way to regulate the crystallization behavior, and therefore the morphology of the material. We focus on metastable solutions of poly(3-hexylthiophene) (P3HT) dissolved in mixtures of m-xylene, a marginal solvent, and chlorobenzene, a good solvent. Appropriate levels of supersaturation are identified to suppress homogenous nucleation of crystals at room temperature, while allowing for crystallization on heterogeneous nucleation sites. We show that in these metastable solutions, P3HT selectively crystallizes on graphene-coated surfaces. Through in situ atomic force microscopy, we confirm that nanowires grow vertically in a face-on orientation from highly oriented pyrolytic graphite and graphene. Moreover, this method can be successfully extended to other conjugated polymers with superior electronic properties, such as poly[2,5-bis(3-tetradecylthiophen-2-yl)thieno[3,2-b] thiophene]. Therefore, this method is a promising route to improve the performance of organic electronics.

  5. High Energy Density Polymer Film Capacitors

    DTIC Science & Technology

    2006-10-01

    are formed by vapor deposition of multifunctional acrylate monomers that are deposited on the PVDF as a thin liquid film and are cross linked using...the world. Vacuum Depositing Inc. American Thin Films Vapor Technologies Inc. 1294 Old Fern Valley Road 2010 East Hennepin Ave. Boulder Tech Center...78 5.5.1 Capacitors Values, Voltage Breakdown, and Energy Density ................ 79 APPENDIX A PVDF AND PET FILMS

  6. Charge transport across the metal-polymer film boundary

    NASA Astrophysics Data System (ADS)

    Yumaguzin, Yu. M.; Salikhov, T. R.; Shayakhmetov, R. U.; Salikhov, R. B.

    2016-08-01

    Thin polyaniline films were fabricated by thermal vacuum evaporation from a Knudsen effusion cell. The conducting properties of films synthesized under different evaporation conditions were studied. The enhancement of the emission capacity of a wolfram tip coated with a polyaniline film of a nanometer thickness was demonstrated experimentally. A model of the discovered effect was proposed. The obtained Fowler-Nordheim current-voltage characteristics were used to estimate the change in the electronic work function occurring when a thin film is deposited on the tip surface. The effective temperature of electrons emitted from the polyaniline film was determined based on the results of analysis of energy distributions, and the specific features of charge transport in the metal-polyaniline-vacuum system were examined. A model of energy bands of the metal-polymer film contact was also constructed.

  7. Simple push coating of polymer thin-film transistors

    NASA Astrophysics Data System (ADS)

    Ikawa, Mitsuhiro; Yamada, Toshikazu; Matsui, Hiroyuki; Minemawari, Hiromi; Tsutsumi, Jun'ya; Horii, Yoshinori; Chikamatsu, Masayuki; Azumi, Reiko; Kumai, Reiji; Hasegawa, Tatsuo

    2012-11-01

    Solution processibility is a unique advantage of organic semiconductors, permitting the low-cost production of flexible electronics under ambient conditions. However, the solution affinity to substrate surfaces remains a serious dilemma; liquid manipulation is more difficult on highly hydrophobic surfaces, but the use of such surfaces is indispensable for improving device characteristics. Here we demonstrate a simple technique, which we call ‘push coating’, to produce uniform large-area semiconducting polymer films over a hydrophobic surface with eliminating material loss. We utilize a poly(dimethylsiloxane)-based trilayer stamp whose conformal contact with the substrate enables capillarity-induced wetting of the surface. Films are formed through solvent sorption and retention in the stamp, allowing the stamp to be peeled perfectly from the film. The planar film formation on hydrophobic surfaces also enables subsequent fine film patterning. The technique improves the crystallinity and field-effect mobility of stamped semiconductor films, constituting a major step towards flexible electronics production.

  8. A Large-Bandgap Conjugated Polymer for Versatile Photovoltaic Applications with High Performance.

    PubMed

    Zhang, Maojie; Guo, Xia; Ma, Wei; Ade, Harald; Hou, Jianhui

    2015-08-19

    A new copolymer PM6 based on fluorothienyl-substituted benzodithiophene is synthesized and characterized. The inverted polymer solar cells based on PM6 exhibit excellent performance with Voc of 0.98 V and power conversion efficiency (PCE) of 9.2% for a thin-film thickness of 75 nm. Furthermore, the single-junction semitransparent device shows a high PCE of 5.7%.

  9. Synthesis and Characterization of Conjugated Polymers and Small Molecules for Organic Photovoltaic Devices

    NASA Astrophysics Data System (ADS)

    Kwon, Obum

    Solar energy harvested directly from sunlight using photovoltaic (PV) technology has become one of the most promising ways to meet growing global energy needs with a sustainable resource while minimizing environmental concerns. Especially, organic bulk heterojunction (BHJ) solar cells have been attracting a great deal of interest as a source of renewable energy because of their potential as low-cost, flexible, light-weight and large-scale devices. The choice of materials in a BHJ solar cell is very important for device performance because the power conversion efficiencies (PCEs) are determined by their some crucial characteristics such as energy levels, charge transfer mobilities and structural orders. In this dissertation, two carbazole-diketopyrrolopyrrole based conjugated polymers (P1 and P2) and three thieno-[3,4-c]pyrrole-4,6-dione (TPD) based small molecules (M1, SM1 and SM2) were synthesized and characterized to investigate their optical, electrical and photovoltaic properties. First, the substitution of alkyl and aryl side chains on the carbazole moiety of two push-pull conjugated polymers (P1 and P2) shows the significant differences in the optical, electrical and photovoltaic properties. Second, TPD-based conjugated small molecule with a donor-acceptor-donor-acceptor-donor (D-A-D-A-D) framework, M1 shows the relatively deep HOMO level resulting the relatively high Voc.(0.85 eV) Small molecule BHJ solar cells were fabricated and characterized using different M1:PC71BM blend ratios, solvents, and additives and the highest PCE achieved in this study was 1.86%. Lastly, different bridgehead atoms of SM1 and SM2 can affect their energy band levels and device performances. The PCE (2.5%) of the SM2-based SM-BHJ solar cell was higher than that of the SM1-based SM-BHJ solar cell (1.5%).

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

    SciTech Connect

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

    2000-03-20

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

  11. Vacuum deposited polymer films: Past, present, and future applications

    SciTech Connect

    Affinito, J.; Martin, P.; Gross, M.; Bennett, W.

    1994-11-01

    Two extremely high rate processes have been developed for the vacuum deposition of polymer thin films. Dubbed the PML (for Polymer Multi-Layer) and LML (for Liquid Multi-Layer) processes, the PML technique was originally developed for the manufacture of polymer/aluminum surface mount capacitors while the LML method arose from a need to fabricate lithium polymer batteries. These processes have since been found to be compatible with most other vacuum deposition techniques in, integrated, in-line coating processes. Battelle has developed an extensive program, and a great deal of hardware, to pursue a wide variety of PML and LML applications which integrate these two process technologies with other, conventional, vacuum deposition methods. The historical development of the technologies is reviewed and the Battelle PML/LML facilities are described. Current Battelle work involving solar thermal control films, PML QWOTs, and polymer/metal high reflectors are also discussed. Battelle PML work that is just starting, involving non-linear optical materials/devices, lithium polymer battery fabrication, electrochromic devices, and polymer/oxide multilayers, is discussed as well.

  12. Methodologies for Controlled Conjugated Polymer Synthesis and Characterization of Small Molecule Organic Semiconductors

    NASA Astrophysics Data System (ADS)

    Bakus, Ronald C., II

    Conjugated polymers can broadly be described as materials which have a structure composed of repeating monomeric units that show extended electronic communication along the backbone. The extended pi-conjugated nature of these materials gives them a set of unique electronic and optical properties, and has lead to their application in a multitude of various technologies. Of specific interest is the application of these materials in various organic electronics applications, such as solution processed plastic solar cells, light emitting diodes, and field effect transistors. Herein is described the synthesis of a class of well-defined, highly active organometallic initiators for use in controlled polymer synthesis. The polymers prepared using the nickel based initiators in Grignard metathesis polymerization posses the following characteristics: rapid generation of high molecular weight polymers, low polydispersity, linear relation between monomer conversion and molecular weight growth, and the selective transfer of an initiating moiety from the organometallic initiator to one polymer chain end. This initiator was then used to prepare a new class of biosensor materials wherein the polymer had a well defined biosensing end group. Additionally, a series of small molecule donors have been developed that have shown promise in a wide variety of organic electronic applications. These materials can broadly be described as having a D'ADAD' type structure where D, D', and A correspond to electron rich and electron deficient aromatic heterocycles, respectively. By tuning the identity of these groups and the side-chains attached to them, one can subtly influence the optical, electronic, and physical properties of the materials. These materials were investigated via single crystal x-ray diffraction studies to gain insight into how changes to the molecule structure such as heteroatom regioisomerism and isoelectronic substitutions effected the molecular structure. These changes in

  13. Synthesis and evaluation of optical and electrochemical properties of a new conjugated polymer containing substituted thiophene and non-conjugation linkers

    SciTech Connect

    R, Prashanth Kumar K D, Udayakumar; K, Siji Narendran N; K, Chandrasekharan

    2014-10-15

    Conjugated polymers have been developed in a variety of applied fields owing to their promising optoelectronic properties. These are pursuing considerable interest as opto-electrical material because of their chemical stability and processability. This paper describes the synthesis and study of electro-optical properties of a new donoracceptor polymer composed of substituted thiophene and 4,4′-propane-2,2-diyldiphenol units as electron rich moieties and 1,3,4-oxadiazole unit as electron deficient moiety. The optical properties of the polymer are studied using UV-visible absorption spectroscopy and fluorescent emission spectroscopy. From the electrochemical data, HOMO and LUMO energy levels of the polymer are calculated.

  14. Surfactant-free, low band gap conjugated polymer nanoparticles and polymer:fullerene nanohybrids with potential for organic photovoltaics

    NASA Astrophysics Data System (ADS)

    Wang, Suxiao; Singh, Amita; Walsh, Nichola; Redmond, Gareth

    2016-06-01

    Stable, aqueous dispersions of nanoparticles based on the low band gap polymers poly [2,7-(9,9-dioctyl-fluorene)-alt-5,5-(4‧,7‧-di-2-thienyl-2‧,1‧,3‧-benzothiadiazole)] (APFO-3) and poly [N-9‧-heptadecanyl-2,7-carbazole-alt-5,5-(4‧,7‧-di-2-thienyl-2‧,1‧,3‧-benzothiadiazole)] (PCDTBT) were prepared, using a flexible, surfactant-free reprecipitation method, and characterized by a variety of optical techniques. Light scattering measurements indicated average nanoparticle hydrodynamic diameters of approximately 40 nm. The particles presented wide-bandwidth absorption and photoluminescence excitation spectra with high absorption cross-sections on the order of 10-12 cm2. Nanoparticle emission spectra were significantly red-shifted, with decreased emission quantum yields and lifetimes, consistent with increased inter-polymer chain interactions in the condensed phase. Single particle photoluminescence studies highlighted the multi-chromophoric nature of the polymer nanoparticles and confirmed their favorable photostabilities. When the nanoparticles were doped with [6,6]-phenyl-C61-butyric acid methyl ester (PCBM), the correspondence of photoluminescence emission quenching, quantum yield decreases, emission lifetime shortening, and increased non-radiative rates with increasing PCBM concentration suggested efficient photo-induced donor-to-acceptor charge transfer between the conjugated polymers and the fullerene dopants co-localized in the nanoparticle cores. Taken together, the data suggest that these surfactant-free hybrid nanomaterials may be useful for integration with future nanostructured organic photovoltaics technologies.

  15. Measuring the Thickness and Elastic Properties of Electroactive Thin-Film Polymers Using Platewave Dispersion Data

    NASA Technical Reports Server (NTRS)

    Bar-Cohen, Yoseph; Lih, Shyh-Shiuh; El-Azab, A.; Mal, Ajit K.

    1996-01-01

    Electroactive thin-film polymers are candidate sensors and actuators materials. They are also finding significant potential in muscle mechanisms and microelectromechanical systems (MEMS). In these applications, polymer thin films of thickness varying between 20 and 300 micrometers are utilized. The authors are currently studying the potential use of platewave dispersion curve measurements as an effective gauging tool for electroactive thin-film polymers.

  16. Conductivity Studies in PVA-PEO-PEG Blended Polymer Films Complexed with Silver Salt

    NASA Astrophysics Data System (ADS)

    Joge, Prajakta; Kanchan, D. K.; Sharma, Poonam; Gondaliya, Nirali

    2011-07-01

    The PVA-PEO blended polymer films complexed with silver nitrate salt and PEG plasticizer were prepared by solution cast technique. The prepared polymer films are characterized by XRD, DSC and impedance spectroscopy. The electrical properties of the blended plasticized polymer films have been discussed.

  17. Ferritin-Polymer Conjugates: Grafting Chemistry and Integration into Nanoscale Assemblies

    SciTech Connect

    Y Hu; D Samanta; S Parelkar; S Hong; Q Wang; T Russell; T Emrick

    2011-12-31

    Controlled free radical polymerization chemistry is used to graft polymer chains to the corona of horse spleen ferritin (HSF) nanocages. Specifically, poly(methacryloyloxyethyl phosphorylcholine) (polyMPC) and poly(PEG methacrylate) (polyPEGMA) chains are grafted onto the nanocages by atom transfer radical polymerization (ATRP), in which the molecular weight of the polymer grafts is controlled by the monomer-to-initiator feed ratio. PolyMPC and polyPEGMA-grafted ferritin show a generally suppressed inclusion into diblock copolymer films relative to native ferritin, and the polymer coating is seen to mask the ferritin nanocages from antibody recognition. The solubility of polyPEGMA-coated ferritin in organic solvents enables its processing with polystyrene-block-poly(ethylene oxide) copolymers, and selective integration into the PEO domains of microphase-separated copolymer structures.

  18. 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

    PubMed Central

    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

  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.

    PubMed

    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. Role of solution structure in self-assembly of conjugated block copolymer thin films

    DOE PAGES

    Brady, Michael A.; Ku, Sung -Yu; Perez, Louis A.; ...

    2016-10-24

    Conjugated block copolymers provide a pathway to achieve thermally stable nanostructured thin films for organic solar cells. We characterized the structural evolution of poly(3-hexylthiophene)-block-poly(diketopyrrolopyrrole–terthiophene) (P3HT-b-DPPT-T) from solution to nanostructured thin films. Aggregation of the DPPT-T block of P3HT-b-DPPT-T was found in solution by small-angle X-ray scattering with the P3HT block remaining well-solvated. The nanostructure in thin films was determined using a combination of wide and small-angle X-ray scattering techniques as a function of processing conditions. The structure in solution controlled the initial nanostructure in spin-cast thin films, allowing subsequent thermal annealing processes to further improve the ordering. In contrast tomore » the results for thin films, nanostructural ordering was not observed in the bulk samples by small-angle X-ray scattering. Finally, these results suggest the importance of controlling solvent induced aggregation in forming nanostructured thin films of conjugated block copolymers.« less

  1. Role of solution structure in self-assembly of conjugated block copolymer thin films

    SciTech Connect

    Brady, Michael A.; Ku, Sung -Yu; Perez, Louis A.; Cochran, Justin E.; Schmidt, Kristin; Weiss, Thomas M.; Toney, Michael F.; Ade, Harald; Hexemer, Alexander; Wang, Cheng; Hawker, Craig J.; Kramer, Edward J.; Chabinyc, Michael L.

    2016-10-24

    Conjugated block copolymers provide a pathway to achieve thermally stable nanostructured thin films for organic solar cells. We characterized the structural evolution of poly(3-hexylthiophene)-block-poly(diketopyrrolopyrrole–terthiophene) (P3HT-b-DPPT-T) from solution to nanostructured thin films. Aggregation of the DPPT-T block of P3HT-b-DPPT-T was found in solution by small-angle X-ray scattering with the P3HT block remaining well-solvated. The nanostructure in thin films was determined using a combination of wide and small-angle X-ray scattering techniques as a function of processing conditions. The structure in solution controlled the initial nanostructure in spin-cast thin films, allowing subsequent thermal annealing processes to further improve the ordering. In contrast to the results for thin films, nanostructural ordering was not observed in the bulk samples by small-angle X-ray scattering. Finally, these results suggest the importance of controlling solvent induced aggregation in forming nanostructured thin films of conjugated block copolymers.

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

    PubMed

    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.

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

    NASA Astrophysics Data System (ADS)

    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.

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

    SciTech Connect

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

    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.

  5. Micro-indentation relaxation measurements in polymer thin films

    NASA Astrophysics Data System (ADS)

    Shinozaki, D. M.; Lu, Y.

    1997-07-01

    A micro-indenter consisting of a piezo-electric driven flat cylindrical punch has been used to measure the dynamic mechanical properties of polystyrene films as thin as 50 μm. The measured viscoelastic response was sensitive to the bonding of the polystyrene to an underlying silicon substrate for films which were thinner than one indenter diameter. The instrument therefore was shown to have practical use in measuring the dynamic mechanical response of polymer films, and the strength of bonding between disparate materials.

  6. Polymer interdiffusion and mechanical property development during latex film formation

    SciTech Connect

    Fu, Z.; Boczar, E.M.; Kirk, A.B.

    1995-12-31

    The interdiffusion of polymer chains across the latex boundaries during latex film formation has been studied using the fluorescence technique of direct energy transfer (DET) or small-angle neutron scattering technique (SANS) by several groups. The increase in mechanical strength and the interdiffusion depth determined by SANS has been correlated for several polystyrene latex systems during film formation. In this paper, we will present the correlation between the increase in mechanical strength and the interdiffusion depth for a poly (amyl methacrylate) latex system. Volume fractions of mixing (Fm) as a function of annealing time for two poly (amyl methacrylate) latex blend films were measured.

  7. Solution-Processable Hyperbranched Conjugated Polymer Nanoparticles Based on C3h -Symmetric Benzotrithiophene for Polymer Solar Cells.

    PubMed

    Wu, Xiaofu; Zhang, Zijian; Hang, Hao; Chen, Yonghong; Xu, Yuxiang; Tong, Hui; Wang, Lixiang

    2017-02-21

    The development of photovoltaic polymers based on C3h -symmetric benzotrithiophene (C3h -BTT), an analogue of the well-known benzodithiophene (BDT) donor unit, has been severely limited due to difficult processability. Here the authors report the preparation of solution-processable C3h -BTT-based hyperbranched conjugated polymer nanoparticles (BTT-HCPNs) with tunable particle sizes via Stille miniemulsion polymerization. Compared with the corresponding star-shaped small molecule (C3h -BTT core with three diketopyrrolopyrrole arms, BTT-3DPP) with a wide bandgap (1.83 eV), both BTT-HCPNs show strong aggregation even in dilute solutions, leading to much-extended absorption (up to ≈1000 nm) and lower bandgaps (1.38 eV). The larger BTT-HCPN particle exhibits stronger aggregation and more extended absorption than the smaller one. As a result, solar cells fabricated from BTT-HCPNs/PC71 BM solutions show a power conversion efficiency up to 1.51% after DIO additive treatment, much higher than that of BTT-3DPP (0.31%).

  8. Bright and efficient blue light-emitting diodes based on conjugated polymer blends

    NASA Astrophysics Data System (ADS)

    Palilis, Leonidas C.; Lidzey, David G.; Redecker, Michael; Bradley, Donal D. C.; Inbasekaran, Michael; Woo, Edmund P.; Wu, Weishi W.

    1999-12-01

    We report on the fabrication and properties of single layer blue light-emitting diodes (LEDs) based on conjugated polymer blends. We have used poly(9,9-dioctylfluorene) (PFO) as the host and a hole transport triarylamine/fluorene copolymer as the guest. Despite the fact that the photoluminescence quantum efficiency of the blend is lower compared than that of the host and guest polymers on their own, an enhancement in both the electroluminescence quantum and power efficiency is seen for the blend. This observation indicates that the hole transport material leads to a significant improvement in hole injection and transport and a greatly improved charge carrier balance factor. A careful comparison of the photoluminescence and the electroluminescence spectra reveals that more emission originates from the guest polymer for electroluminescence than for photoluminescence. This can be rationalized by the expectation that both Forster transfer and charge transfer from the host to the guest occur under electrical operation of the device. Only Forster transfer is expected for optical excitation. A much higher brightness and a lower turn on and operating voltage is achieved for the blend. The emission from our optimized blue single layer LED reaches a maximum brightness of 1550 cd/m2 and has a maximum external quantum efficiency of .4% and a maximum power efficiency of 0.3 lm/W.

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

    NASA Astrophysics Data System (ADS)

    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.

  10. Photophysical and morphological implications of single-strand conjugated polymer folding in solution

    SciTech Connect

    Fauvell, Thomas J.; Zheng, Tianyue; Jackson, Nicholas E.; Ratner, Mark A.; Yu, Luping; Chen, Lin X.

    2016-04-08

    Organic semiconductors have garnered substantial interest in optoelectronics, but their device performances exhibit strong dependencies on material crystallinity and packing. In an effort to understand the interactions dictating the morphological and photophysical properties of a high-performing photovoltaic polymer, PTB7, a series of short oligomers and low molecular weight polymers of PTB7 were synthesized. Chain-length dependent optical studies of these oligomers demonstrate that PTB7’s low-energy visible absorption is largely due to self-aggregation-induced ordering, rather than in-chain charge transfer, as previously thought. By examining molecular weight and concentration dependent optical properties, supplemented by molecular dynamics simulations, we attribute polymeric PTB7’s unique midgap fluorescence and concentration independent absorption spectrum to an interplay between low molecular weight unaggregated strands and high-molecular weight self-aggregated (folded) strands. Specifically, we propose that the onset of PTB7 self-folding occurs between 7 and 13 repeat units, but the aggregates characteristic of polymeric PTB7 only develop at lengths of ~30 repeat units. Atomistic molecular dynamics simulations of PTB7 corroborate these conclusions, and a simple relation is proposed which quantifies the free-energy of conjugated polymer folding. Lastly, this study provides detailed guidance in the design of intra- and interchain contributions to the photophysical and morphological properties of polymeric semiconductors.

  11. Subpicosecond Photon-Energy-Dependent Hole Transfer from PbS Quantum Dots to Conjugated Polymers.

    PubMed

    Colbert, Adam E; Jedlicka, Erin; Wu, Wenbi; Ginger, David S

    2016-12-15

    We use transient absorption (TA) spectroscopy to study the origin of photon-energy dependent hole transfer yields in blends of PbS quantum dots with the conjugated polymer poly(3-hexylthiophene-2,5-diyl) (P3HT). We selectively excite only the quantum dots at two different wavelengths and measure the polymer ground state bleach resulting from the transfer of photoexcited holes. The higher photon-energy pump shows a greater prompt yield of hole transfer compared to the lower photon-energy excitation, on time scales sufficient to out-compete hot carrier cooling in lead chalcogenide quantum dots. We interpret the results as evidence that the excess energy of nonthermalized, or "hot," excitons resulting from higher photon-energy excitation allows more efficient charge transfer to the polymer in these systems. The data also demonstrate slow charge transfer rates, up to ∼1 ns, of the relaxed excitations on the PbS dots. These findings help to clarify the role of excess photon energy and carrier relaxation dynamics on free carrier generation in donor/acceptor solar cells.

  12. Transparent lithiated polymer films for thermal neutron detection

    NASA Astrophysics Data System (ADS)

    Mabe, Andrew N.; Auxier, John D.; Urffer, Matthew J.; Penumadu, Dayakar; Schweitzer, George K.; Miller, Laurence F.

    2013-09-01

    Novel water-soluble 6Li loaded copolymer scintillation films have been designed and fabricated to detect thermal neutrons. Styrene and maleic anhydride were copolymerized to form an alternating copolymer, then the anhydride functionality was hydrolyzed using 6Li hydroxide. The resulting poly(styrene-co-lithium maleate) was mixed with salicylic acid as a fluor and cast as a thin film from water. The maximum 6Li loading obtained that resulted in a transparent film was 4.36% by mass (6Li to polymer). The optimum fluorescence output was obtained for 11.7% salicylic acid by mass, presumably in the form of lithium salicylate, resulting in an optimum film containing 3.85% by mass of 6Li. A facile and robust synthesis method, film fabrication protocol, photoluminescence results, and scintillation responses are reported herein.

  13. Polymer Thin Film Transistors: High Electron Mobility and Ambipolar Charge Transport

    NASA Astrophysics Data System (ADS)

    Jenekhe, Samson; Babel, Amit

    2004-03-01

    Along with high performance unipolar FETs, knowledge of ambipolar charge transport in conjugated polymers and organic semiconductors is important to realize the ultimate vision of all-plastic complementary integrated circuits for logic and memory applications. We present herein studies of electron transport in n-type conjugated ladder polymer, poly(benzobisimidazobenzophenanthroline) (BBL) in which we observed field-effect electron mobilities as high as 0.05-0.1 cm^2/Vs.^[1] We have also developed new ambipolar thin film transistors based on blends of BBL and copper phthalocyanine (CuPc). Ambipolar hole mobilities were as high as 2.0 × 10-4 cm^2/Vs while electron mobilities were up to 3.0 × 10-5 cm^2/Vs. Transmission electron microscopy showed crystallization of CuPc in the α -crystal form within the semicrystalline BBL matrix. On prolonged treatment of the blend FETs in methanol, unipolar hole mobilities as high as 2.0 × 10-3 cm^2/Vs were observed, comparable to hole mobilities in thermally evaporated CuPc FETs. [1] Babel, A.; Jenekhe, S. A. J. Am. Chem. Soc. 2003, 125, 13656.

  14. Co-polymer Films for Sensors

    NASA Technical Reports Server (NTRS)

    Ryan, Margaret A. (Inventor); Homer, Margie L. (Inventor); Yen, Shiao-Pin S. (Inventor); Kisor, Adam (Inventor); Jewell, April D. (Inventor); Shevade, Abhijit V. (Inventor); Manatt, Kenneth S. (Inventor); Taylor, Charles (Inventor); Blanco, Mario (Inventor); Goddard, William A. (Inventor)

    2012-01-01

    Embodiments include a sensor comprising a co-polymer, the co-polymer comprising a first monomer and a second monomer. For some embodiments, the first monomer is poly-4-vinyl pyridine, and the second monomer is poly-4-vinyl pyridinium propylamine chloride. For some embodiments, the first monomer is polystyrene and the second monomer is poly-2-vinyl pyridinium propylamine chloride. For some embodiments, the first monomer is poly-4-vinyl pyridine, and the second monomer is poly-4-vinyl pyridinium benzylamine chloride. Other embodiments are described and claimed.

  15. Co-polymer films for sensors

    NASA Technical Reports Server (NTRS)

    Ryan, Margaret A. (Inventor); Homer, Margie L. (Inventor); Yen, Shiao-Pin S. (Inventor); Kisor, Adam (Inventor); Jewell, April D. (Inventor); Shevade, Abhijit V. (Inventor); Manatt, Kenneth S. (Inventor); Taylor, Charles (Inventor); Blanco, Mario (Inventor); Goddard, William A. (Inventor)

    2010-01-01

    Embodiments include a sensor comprising a co-polymer, the co-polymer comprising a first monomer and a second monomer. For some embodiments, the first monomer is poly-4-vinyl pyridine, and the second monomer is poly-4-vinyl pyridinium propylamine chloride. For some embodiments, the first monomer is polystyrene and the second monomer is poly-2-vinyl pyridinium propylamine chloride. For some embodiments, the first monomer is poly-4-vinyl pyridine, and the second monomer is poly-4-vinyl pyridinium benzylamine chloride. Other embodiments are described and claimed.

  16. Direct observation of athermal photofluidisation in azo-polymer films.

    PubMed

    Hurduc, Nicolae; Donose, Bogdan C; Macovei, Alina; Paius, Cristina; Ibanescu, Constanta; Scutaru, Dan; Hamel, Matthieu; Branza-Nichita, Norica; Rocha, Licinio

    2014-07-14

    The surface relief gratings (SRGs) can be generated when azo-polymer films are exposed to laser beam interference as a result of mass migration. Despite considerable research effort over the past two decades this complex phenomenon remains incompletely understood. Here we show, for the first time, the athermal photofluidisation of azo-polysiloxane films exposed to 488 nm light, directly monitored by optical microscopy. A process of surface relief erasure occurring in parallel with its inscription was also observed during laser irradiation. We therefore propose a new mechanism of SRG formation, based on three different processes: (1) the polymer photo-fluidization in illuminated regions, (2) the mass displacement from illuminated to dark regions and (3) the inverse mass displacement, from dark to illuminated regions. The mechanical properties of the films during UV light irradiation were investigated by classical rheology and, for the first time, by using amplitude modulation-frequency modulation atomic force microscopy (AM-FM AFM).

  17. Studies of Optical Wave Front Conjugation and Imaging Properties of Nematic Liquid Crystal Films

    DTIC Science & Technology

    1988-06-30

    processes was also demonstrated. The capability of optical four wave mixing to generate amplified reflection and self- oscillation in nematic liquid crystal...via real time optical wave mixing process was also demonstrated. The capability of optical four wave mixing to generate amplified reflection and self...the special nonlinear optical properties of liquid crystal films for optical wave front conjugation and in related four -wave mixing processes. The

  18. Anti-biofouling properties of amphiphilic phosphorylcholine polymer films.

    PubMed

    Li, Yan; Liu, Cheng-Mei; Yang, Jin-Ying; Gao, Ya-Hui; Li, Xue-Song; Que, Guo-He; Lu, J R

    2011-07-01

    Surfaces of amphiphilic phosphorylcholine polymer (PC1036) prepared by spin-coating were characterized by spectroscopic ellipsometry, water contact angle and atomic force microscopy. The antifouling properties of the PC1036 films to marine benthic diatom Nitzschia closterium MMDL533 were also investigated. The results showed that the dry PC1036 film promoted the adhesion of N. closterium MMDL533 because the hydrophobic lauryl groups were present in the film surface. The 2 h-swelled PC1036 films had excellent anti-fouling properties with extremely low attachment densities and retention densities no matter what the annealing temperature was. The thickness of the coated films lower than 147 Å had a profound effect on the film anti-fouling properties. Otherwise, when the film thickness was higher than that value, there was no more improvement of diatom cell reduction observed. The annealing temperature had only a little effect on the film resistant to diatom adhesion, which might be attributed to two factors including the PC group packing densities in the outer PC layer and the equilibrated water volume fraction in the 2 h-swelled PC1036 films.

  19. A brief perspective on the evolution of plastic electronics--from highly conducting polymers to conjugated organic semiconductors.

    PubMed

    Skabara, Peter J

    2013-10-18

    This Viewpoint reflects on the work published in J. Chem. Soc., Chem. Commun. in 1977 by the Nobel Prize winners Shirakawa, MacDiarmid and Heeger. This paper, which is one of the most cited ChemComm articles of all time, motivated the rapid development of conducting (conjugated) polymers and the birth of plastic electronics.

  20. Thin film conductive polymer for microactuator and micromuscle applications

    SciTech Connect

    Lee, A.P.; Hong, K.; Trevino, J.; Northrup, M.A.

    1994-04-14

    Conductive polymer/polyimide bimorphic microcantilevers have been actuated vertically (out-of-plane) upon the volumetric changes induced by electrochemical doping of the polymer. The microcantilevers that are 200-500 {mu}m in length and 50-100 {mu}m in width can be fully extended from a circularly-curled geometry, and thus generate more than 100 {mu}m displacement. Dynamically the microcantilevers have been driven as fast as 1.2 Hz and the polymer was stable for over a week stored in air and light. Residual stresses in the polymer film is estimated to be as high as 254 MPa, and actuation stresses are as high as 50 MPa.

  1. Synthesis and characteristics of metal-phthalocyanine-polymer composite films

    NASA Astrophysics Data System (ADS)

    Chen, Jianming; Zhang, Jiancheng; Shen, Yue; Liu, Xiuhong

    2000-11-01

    Fe(III)-2,9,16,23-tertracarboxy-phthalocyanine (Fe (III)- taPc) was synthesized, and was bonded to polystyrene (PS) with covalence by Friedel-Crafts reaction to form a new polymer [Fe (111)-taPc-PS] [polymer (II)]. Uv-Vis and Infrared spectra indicated that Fe (III)-taPc was successfully bonded to PS. A photoreceptor device of sandwich structure consisting of alternate layers of polymer (II) and fullerene (C60) was prepared. The experiment results show that the photoconductivity of the photoreceptor is higher than that of the single-layer film of polymer (II) or C60, because of the charge-transfer effect between the layers.

  2. High aspect ratio conjugated polymer nanowires for high performance field-effect transistors and phototransistors.

    PubMed

    Um, Hyun Ah; Lee, Dae Hee; Heo, Dong Uk; Yang, Da Seul; Shin, Jicheol; Baik, Hionsuck; Cho, Min Ju; Choi, Dong Hoon

    2015-05-26

    We synthesized a highly crystalline DPP-based polymer, DPPBTSPE, which contained 1,2-bis(5-(thiophen-2-yl)selenophen-2-yl)ethene as a planar and rigid electron donating group. High- and low-molecular weight (MW) DPPBTSPE fractions were collected by Soxhlet extraction and were employed to investigate their unique charge transport properties in macroscopic films and single crystalline polymer nanowire (SC-PNW), respectively. The low-MW polymer could provide well-isolated and high aspect ratio SC-PNWs, in which the direction of π-π stacking was perpendicular to the wire growing axis. The field effect transistors made of SC-PNWs exhibited remarkably high carrier mobility of 24 cm(2) V(-1) s(-1). In addition, phototransistors (PTs) made of SC-PNW showed very high performance in terms of photoresponsivity (R) and photoswitching ratio (P). The average R of the SC PNW-based PTs were in the range of 160-170 A W(-1) and the maximum R was measured at 1920 A W(-1), which is almost three orders higher than that of thin film-based PT device.

  3. Surface analysis of the selective excimer laser patterning of a thin PEDOT:PSS film on flexible polymer films

    NASA Astrophysics Data System (ADS)

    Schaubroeck, David; De Smet, Jelle; Willems, Wouter; Cools, Pieter; De Geyter, Nathalie; Morent, Rino; De Smet, Herbert; Van Steenbeerge, Geert

    2016-07-01

    Fast patterning of highly conductive polymers like PEDOT:PSS (poly (3,4-ethylene dioxythiophene): polystyrene sulfonate) with lasers can contribute to the development of industrial production of liquid crystal displays on polymer foils. In this article, the selective UV laser patterning of a PEDOT:PSS film on flexible polymer films is investigated. Based on their optical properties, three polymer films are investigated: polyethylene terephthalate (PET), polymethyl methacrylate (PMMA) and cellulose triacetate (TAC). Ablation parameters for a 110 nm PEDOT:PSS film on these polymer films are optimized. A detailed study of the crater depth, topography and surface composition are provided using optical profilometry, scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS), respectively. The electrical insulation of the lines is measured and correlated to the crater analyses for different laser settings. Finally, potential ablation parameters for each of the polymer films are derived.

  4. Metallic waveguide mirrors in polymer film waveguides

    NASA Astrophysics Data System (ADS)

    Wolff, S.; Giehl, A. R.; Renno, M.; Fouckhardt, H.

    2001-10-01

    A technology for the fabrication of metallic waveguide mirrors is developed. Plane and curved waveguide mirrors, the latter acting in the same way as cylindrical lenses, are realized in benzocyclobutene (BCB) film waveguides. The waveguide mirror structure is dry-etched into the BCB film waveguide. To enhance the reflectivity of the waveguide mirrors, the waveguide edge is metallized. The BCB film waveguide mirrors are characterized with respect to waveguide attenuation and mirror reflectivity. The waveguide attenuation of the processed BCB waveguide is 0.5 dB/cm. Ag-coated BCB waveguide mirrors show a reflectivity of 71%. The efficiency of total internal reflection (TIR, i.e. in the case without metallization) at the dry-etched waveguide edge is 74%. As an application of the BCB waveguide mirrors a hybrid integrated optical module for Fourier-optical transverse mode selection in broad area lasers (BAL) is proposed.

  5. Structural Typing of Systemic Amyloidoses by Luminescent-Conjugated Polymer Spectroscopy

    PubMed Central

    Nilsson, K. Peter R.; Ikenberg, Kristian; Åslund, Andreas; Fransson, Sophia; Konradsson, Peter; Röcken, Christoph; Moch, Holger; Aguzzi, Adriano

    2010-01-01

    Most systemic amyloidoses are progressive and lethal, and their therapy depends on the identification of the offending proteins. Here we report that luminescent-conjugated thiophene polymers (LCP) sensitively detect amyloid deposits. The heterodisperse polythiophene acetic acid derivatives, polythiophene acetic acid (PTAA) and trimeric PTAA, emitted yellow-red fluorescence on binding to amyloid deposits, whereas chemically homogeneous pentameric formic thiophene acetic acid emitted green-yellow fluorescence. The geometry of LCPs modulates the spectral composition of the emitted light, thereby reporting ligand-induced steric changes. Accordingly, a screen of PTAA-stained amyloid deposits in histological tissue arrays revealed striking spectral differences between specimens. Blinded cluster assignments of spectral profiles of tissue samples from 108 tissue samples derived from 96 patients identified three nonoverlapping classes, which were found to match AA, AL, and ATTR immunotyping. We conclude that LCP spectroscopy is a sensitive and powerful tool for identifying and characterizing amyloid deposits. PMID:20035056

  6. Optical tuning of the fluorescence spectrum of a π-conjugated polymer through excitation power.

    PubMed

    Deichmann, Vitor Angelo Fonseca; Yakutkin, Vladimir; Baluschev, Stanislav; Akcelrud, Leni

    2011-05-26

    The photophysical properties of a π-conjugated polymer containing 2,2'-bipyridyl alternated with 2,5-dihexyloxyphenylene units (PBPyDHP) are investigated experimentally in terms of the conditions used (solvent, concentration, presence or absence of molecular oxygen, and optical excitation power). The experimental results have suggested that the fluorescence from PBPyDHP can be tuned by proper selection of the experimental conditions showing only one or two emission peaks: 445 nm (blue) and 555 nm (green). The observed effects were interpreted in terms of the twisted intramolecular charge transfer (TICT) theory. This is the first experimental report showing the interconversion of an usual fluorescence, called locally emission state (LE), to a TICT state in second scale time by varying the excitation power; that is, even though the torsion of only one fluorophore occurs in a nano or picosecond scale, the global change (the interconversion for all fluorophores) has occurred in the second time scale.

  7. Core shell hybrids based on noble metal nanoparticles and conjugated polymers: synthesis and characterization

    NASA Astrophysics Data System (ADS)

    Fratoddi, Ilaria; Venditti, Iole; Battocchio, Chiara; Polzonetti, Giovanni; Cametti, Cesare; Russo, Maria Vittoria

    2011-12-01

    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.

  8. Synthesis of a new conjugated polymer for DNA alkylation and gene regulation.

    PubMed

    Nie, Chenyao; Zhu, Chunlei; Feng, Liheng; Lv, Fengting; Liu, Libing; Wang, Shu

    2013-06-12

    A new polyfluorene derivative containing pendent alkylating chlorambucil (PFP-Cbl) was synthesized and characterized. Under direct incubation with DNA in vitro, PFP-Cbl could undergo an efficient DNA alkylating reaction and induce DNA cross-linking. In vitro transcription and translation experiment exhibited that the PFP-Cbl significantly down-regulated the gene expression of luciferase reporter plasmid. The down-regulation of gene expression was also verified through the transfection experiment of p-EGFP plasmid, which showed decreased green fluorescent protein (GFP) in cells. Meanwhile, the self-luminous property of PFP-Cbl could make it able to trace the internalized PFP-Cbl and plasmid complexes resulted from cross-linking in cells by fluorescent microscopy. Combining the features of alkylating function, multivalent binding sites, and fluorescent characteristics, PFP-Cbl provides a new insight in the area of gene regulation and extends the new applications of conjugated polymers (CPs).

  9. Anodic, cathodic, and annihilation electrochemiluminescence emissions from hydrophilic conjugated polymer dots in aqueous medium.

    PubMed

    Dai, Ruiping; Wu, Fanmin; Xu, Huifeng; Chi, Yuwu

    2015-07-22

    Hydrophilic poly[2-methoxy-5-(2-ethylhexyloxy)-1,4-phenylenevinylene] (MEH-PPV) conjugated polymer dots (CP-dots) capped by Triton X-100 were synthesized. For the first time, the electrochemiluminescence (ECL) emission of CP-dots was investigated in aqueous solution. At the glassy carbon/water interface, the CP-dots have excellent and multichannel ECL properties, such as having annihilation ECL activity in the absence of coreactants, and give bright anodic and cathodic ECL emission (590 nm) in the presence of tri-n-propylamine (TPrA) and peroxydisulfate (S2O8(2-)), respectively. The versatile ECL properties of the hydrophilic CP-dots combined with their low cytotoxicity, good biocompatibility, and easy bioconjugation may suggest promising applications of this new type of ECL nanomaterial in novel biosensing and bioimaging, and new types of light-emitting devices.

  10. A luminescent coordination polymer based on a π-conjugated ligand: Syntheses, structure and luminescent property

    NASA Astrophysics Data System (ADS)

    Li, Dan-Yang; Xie, Hua; Yao, Xiao-Qiang; Ma, Heng-Chang; Lei, Zi-Qiang; Liu, Jia-Cheng

    2017-04-01

    A new cadmium coordination polymer [Cd(DPFE)(adip)0.5(NO3)]n (1) has been synthesized hydrothermally from the self-assembly of the Cd2+ ion with a new π-conjugated rigid ligand DPFE and the adipic acid, where DPFE = 2,7-di(pyridin-4-yl)-9H-fluorene and H2adip = adipic acid. The structure of 1 was full characterized by elemental analysis, FT-IR spectroscopy and single crystal X-ray diffraction. Structural analysis reveals compound 1 is a dinuclear Cd(II) based two-dimensional (4,4) layer and two kinds of strong intramolecular π-π stacking interactions exist between pyridyl rings and benzene rings. In addition, the thermogravimetric analysis and solid-state luminescent properties have also been investigated.

  11. Pd-catalysed direct arylation polymerisation for synthesis of low-bandgap conjugated polymers and photovoltaic performance.

    PubMed

    Chang, Shu-Wei; Waters, Huw; Kettle, Jeff; Kuo, Zi-Rui; Li, Chun-Han; Yu, Chin-Yang; Horie, Masaki

    2012-11-23

    Low-bandgap conjugated copolymers based on a donor-acceptor structure have been synthesised via palladium-complex catalysed direct arylation polymerisation. Initially, we report the optimisation of the synthesis of poly(cyclopentadithiophene-alt-benzothiadiazole) (PCPDTBT) formed between cyclopentadithiophene and dibromobenzothiadiazole units. The polymerisation condition has been optimised, which affords high-molecular-weight polymers of up to M(n) = 70 k using N-methylpyrrolidone as a solvent. The polymers are used to fabricate organic photovoltaic devices and the best performing PCPDTBT device exhibits a moderate improvement over devices fabricated using the related polymer via Suzuki coupling. Similar polymerisation conditions have also been applied for other monomer units.

  12. Multilevel conductance switching in polymer films

    NASA Astrophysics Data System (ADS)

    Lauters, M.; McCarthy, B.; Sarid, D.; Jabbour, G. E.

    2006-07-01

    Multilevel conductance switching in poly[2-methoxy-5-(2'-ethyl-hexyloxy)-1,4-phenylene vinylene] (MEH-PPV) films is demonstrated. A thin-film structure, ITO-coated glass/MEH-PPV/Al, has shown the ability to store a continuum of conductance states. These states are nonvolatile and can be switched reproducibly by applying appropriate programing biases above a certain threshold voltage. The electrical conductivity of the highest and lowest states can differ by five orders of magnitude. Furthermore, these devices exhibit good cyclic switching characteristics and retention times of several weeks.

  13. Updated evaluation of polymer films for electrical insulation

    SciTech Connect

    McCoy, H.E. Jr.

    1990-08-01

    Several types of tests have been run on polymer film materials that could be useful for electrical insulation. The polymers studied were polyethylene terephtalate, polycarbonate, polysulfone, polyetherimide, ultrahigh-molecular-weight polyethylene, polyimide, polybutylene terephthalate, and a laminate of Kraft paper and polypropylene. Thermal aging tests were run to 60,000 h on several of the polymers, and the samples were evaluated by tensile tests, electrical breakdown tests, and immersion density measurements. Because of the wide range of potential service conditions, tensile tests were run on as-received materials over the temperature range of {minus}196 to 200{degree}C. Polyimide is probably the only material suitable for the extremes of this temperature range, but many of the other polymers would be suitable for intermediate temperatures. Creep tests were run in nitrogen and transformer oil at 90{degree}C. It was found that some polymers are weaker and less ductile in oil than in nitrogen and that other polymers have equivalent properties in the two environments. A means of applying mechanical, thermal, and electrical stresses simultaneously to polymer samples was developed. Tests were run at 90{degree}C in transformer oil on polyethylene terephthalate, polyimide, and polyethersulfone. Tests thus far do not indicate that the creep rate is affected by the application of a 5 kV dc potential. 7 refs., 30 figs., 16 tabs.

  14. In situ growth of side-chain PEG polymers from functionalized human growth hormone-a new technique for preparation of enhanced protein-polymer conjugates.

    PubMed

    Magnusson, Johannes Pall; Bersani, Sara; Salmaso, Stefano; Alexander, Cameron; Caliceti, Paolo

    2010-04-21

    The application of atom transfer radical polymerization (ATRP) for preparation of a novel class of protein-polymer bioconjugates is described, exemplified by the synthesis of a recombinant human growth hormone (rh-GH) poly(ethylene glycol) methyl ether methacrylate (PEGMA) hybrid. The rh-GH protein was activated via a bromo-ester functionalized linker and used as a macroinitiator to polymerize the hydrophilic monomer PEGMA under solely aqueous conditions at 4 degrees C. ATRP conditions resulted in controlled polymer growth from rh-GH with low-polydispersity polyPEGMA chains. The rh-GH PEGMA product exhibited properties consistent with the presence of attached hydrophilic polymer chains, namely, high stability to denaturation and proteolysis. The polymerization conditions and conjugation proceeded with retention of the biological activity of the hormone. The rh-GH PEGMA was administered subcutaneously to rats and the activity compared to native rh-GH. The rh-GH PEGMA exhibited similar activity as the native rh-GH in vivo when a daily dose of 40 microg was administered. However, when a higher dose of 120 microg was administered with 3 days between injections the bioavailability of the rh-GH PEGMA was significantly better than that of the native. The results therefore demonstrate that ATRP can be successfully used as a general alternative approach to direct polymer conjugation, namely, PEGylation, to produce PEG-like protein conjugates. This technique can be exploited to design and synthesize protein-polymer derivatives with tailored therapeutic properties.

  15. Parallel, open-channel lateral flow (immuno) assay substrate based on capillary-channeled polymer films.

    PubMed

    Zhang, Lynn X; Jiang, Liuwei; Willett, Daniel R; Marcus, R Kenneth

    2016-02-07

    Presented here is a novel implementation of polypropylene capillary-channeled polymer (C-CP) films, functionalized for bioaffinity separations and implemented as a platform for lateral flow (immuno) assays. The parallel ∼80 μm × 80 μm channels pass test solutions down the 30 mm film length via spontaneous wicking action, setting up the possibility for immobilizing different capture agents in the respective channels. The base-film modification process is divided into two steps: ultraviolet light treatment to improve hydrophillicity of the polypropylene substrate and the physical adsorption of a functionalized lipid tethered ligand (LTL) as a selective capture agent. The entire modification procedure is performed under ambient conditions in an aqueous solution without extreme pH conditions. In this demonstration, physical adsorption of a biotinylated-LTL onto the UV-treated PP surface selectively captures Texas Red-labeled streptavidin (SAv-TR) in the presence of enhanced green fluorescence protein (EGFP), which passes without retention in less than 5 s. In addition to the fluorescence imaging of the protein solutes, matrix assisted laser desorption/ionization-mass spectrometry (MALDI-MS) was used to confirm the formation of the LTL-SAv conjugates on the channel surface as well as to demonstrate an alternative means of probing the capture step. The present effort sets the groundwork for further development of C-CP films as a parallel, multi-analyte LFA platform; a format that to-date has not been described.

  16. Solution-based electrical doping of semiconducting polymer films over a limited depth.

    PubMed

    Kolesov, Vladimir A; Fuentes-Hernandez, Canek; Chou, Wen-Fang; Aizawa, Naoya; Larrain, Felipe A; Wang, Ming; Perrotta, Alberto; Choi, Sangmoo; Graham, Samuel; Bazan, Guillermo C; Nguyen, Thuc-Quyen; Marder, Seth R; Kippelen, Bernard

    2017-04-01

    Solution-based electrical doping protocols may allow more versatility in the design of organic electronic devices; yet, controlling the diffusion of dopants in organic semiconductors and their stability has proven challenging. Here we present a solution-based approach for electrical p-doping of films of donor conjugated organic semiconductors and their blends with acceptors over a limited depth with a decay constant of 10-20 nm by post-process immersion into a polyoxometalate solution (phosphomolybdic acid, PMA) in nitromethane. PMA-doped films show increased electrical conductivity and work function, reduced solubility in the processing solvent, and improved photo-oxidative stability in air. This approach is applicable to a variety of organic semiconductors used in photovoltaics and field-effect transistors. PMA doping over a limited depth of bulk heterojunction polymeric films, in which amine-containing polymers were mixed in the solution used for film formation, enables single-layer organic photovoltaic devices, processed at room temperature, with power conversion efficiencies up to 5.9 ± 0.2% and stable performance on shelf-lifetime studies at 60 °C for at least 280 h.

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

    PubMed

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

    2014-09-21

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

  18. Near-infrared light-triggered thermochemotherapy of cancer using a polymer-gold nanorod conjugate

    NASA Astrophysics Data System (ADS)

    Ko, Hyewon; Son, Soyoung; Bae, Seonghwan; Kim, Joo-Hyung; Yi, Gi-Ra; Park, Jae Hyung

    2016-04-01

    A biocompatible polymer-gold nanorod (P-AuNR) conjugate was developed as a thermo-chemotherapeutic nano-sized drug carrier for cancer therapy using near-infrared (NIR) light as an external trigger. The amphiphilic polymer, poly(ethylene glycol)-block-poly(caprolactone) (PEG-b-PCL) bearing a disulfide bond, was prepared using a facile synthetic route via copper(I)-free click chemistry and covalently linked to AuNR. The chemical structures and successful conjugation of PEG-b-PCL were analyzed using 1H NMR and FT-IR. Doxorubicin (DOX), a hydrophobic anticancer drug, was effectively loaded into the hydrophobic PCL domain of P-AuNR through a simple dialysis method. P-AuNR showed longitudinal plasmon resonance absorption at the NIR region, thus generating heat under irradiation at 808 nm. Interestingly, exposure of P-AuNRs to NIR induced a structural change in the PCL block from a crystalline to an amorphous state, leading to the temporally controlled release of DOX. No significant release of DOX was observed from P-AuNRs under physiological conditions (pH 7.4), whereas the release rate of DOX was remarkably enhanced in response to NIR irradiation. In vitro cellular experiments to assess cytotoxicity and intracellular drug release behavior of DOX-P-AuNRs demonstrated that the release of DOX could be selectively regulated by NIR irradiation. Overall, DOX-P-AuNRs might have the potential to overcome the indiscriminate toxicity of free DOX.

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

    NASA Astrophysics Data System (ADS)

    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

  20. The effect of chain bending on the photophysical properties of conjugated polymers.

    PubMed

    Hestand, Nicholas J; Spano, Frank C

    2014-07-17

    The impact of chain bending on the photophysical properties of emissive conjugated polymers (CPs) is studied theoretically using Holstein-style Hamiltonians which treat vibronic coupling involving the ubiquitous vinyl/ring stretching mode nonadiabatically. The photophysical impact of chain bending is already evident at the level of an effective Frenkel Hamiltonian, where the positive exciton band curvature in CPs translates to negative excitonic coupling between monomeric units, as in J-aggregates. It is shown that the absorption and photoluminescence (PL) spectral line shapes respond very differently to chain bending. The misalignment of monomeric transition dipole moments with bending selectively attenuates the 0-0 PL peak intensity while leaving the 0-1 intensity practically unchanged, a property which is ultimately due to the uniquely coherent nature of the 0-0 peak. Hence, the 0-0/0-1 PL ratio, as well as the radiative decay rate, decrease with chain bending, effects that are more pronounced at lower temperatures where exciton coherence extends over a larger portion of the chain. Increasing temperature and/or static disorder reduces the exciton coherence number, Ncoh, thereby reducing the sensitivity to bending. In marked contrast, the absorption vibronic progression is far less sensitive to morphological changes, even at low temperatures, and is mainly responsive to the exciton bandwidth. The above results also hold when using a more accurate 1D semiconductor Hamiltonian which allows for electron-hole separation along the CP chain. The findings may suggest unique ways of controlling the radiative properties of conjugated polymer chains useful in applications such as organic light emitting diodes (OLEDs) and low-temperature sensors.

  1. Nanostructures of an amphiphilic zinc phthalocyanine polymer conjugate for photodynamic therapy of psoriasis.

    PubMed

    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.

  2. Deformation Hysteresis of Electrohydrodynamic Patterning on a Thin Polymer Film.

    PubMed

    Yang, Qingzhen; Li, Ben Q; Tian, Hongmiao; Li, Xiangming; Shao, Jinyou; Chen, Xiaoliang; Xu, Feng

    2016-07-13

    Electrohydrodynamic patterning is a technique that enables micro/nanostructures via imposing an external voltage on thin polymer films. In this investigation, we studied the electrohydrodynamic patterning theoretically and experimentally, with special interest focused on the equilibrium state. It is found that the equilibrium structure height increases with the voltage. In addition, we have observed, and believe it to be the first time, a hysteresis phenomenon exists in the relationship between the voltage and structure height. With an increase in the voltage, a critical value (the first critical voltage) is noticed, above which the polymer film would increase dramatically until it comes into contact with the template. However, with a decrease in the voltage, a smaller voltage (the second critical voltage) is needed to detach the polymer from the template. The mismatch of the first and second critical voltages distorts the voltage-structure height curve into an "S" shape. Such a phenomenon is verified for three representative templates and also by experiments. Furthermore, the effects of some parameters (e.g., polymer film thickness and dielectric constant) on this hysteresis phenomenon are also discussed.

  3. Nanodiamond-polymer nanoparticle composites and their thin films

    NASA Astrophysics Data System (ADS)

    Attia, N. F.; Rao, J. P.; Geckeler, K. E.

    2014-04-01

    Nanodiamonds obtained from detonation processes have received a great deal of attention during the past decades because of their unique properties and applications. The dispersion of nanodiamond particles can be achieved by different methods including the use of polymer nanoparticles. Here, we describe the dispersion of nanodiamonds in conjunction with sonication using poly(vinylpyrrolidone) nanoparticles with a particle size range of 23.3-61.3 nm, providing a good, economic, and efficient method for the dispersion. The average particle size was found to be 37.5 nm, as confirmed by transmission electron microscopy. The interaction between the nanodiamonds and polymer nanoparticles was characterized by FTIR spectroscopy and the effect of the polymer nanoparticle concentration, sonication time, and frequency on the dispersion process of nanodiamonds is highlighted. In addition, we prepared thin films of nanodiamond-polymer composites with different nanodiamond contents that showed good nanodiamond dispersion. The thin film can act as a UV filter and is transparent in the visible region. The thin films of nanodiamond-poly(vinylpyrrolidone) nanoparticles were characterized by SEM and UV-Vis spectroscopy.

  4. Template-assisted generation of nanocavities within plasma polymer films.

    PubMed

    Vasilev, Krasimir; Casanal, Ana; Challougui, Hela; Griesser, Hans J

    2009-05-21

    The generation of nanosized cavities within thin film layers is of interest for a number of fundamental and applied reasons. One challenge is to make such systems sufficiently robust mechanically. Plasma polymer (pp) films possess excellent mechanical stability if deposition conditions are selected such as to achieve a sufficient density of cross-linking and resistance to extraction of polymeric material by solvents. In this study, gold nanoparticles of 15 and 70 nm diameter were used as sacrificial templates to generate nanocavities in pp films of various thickness values in the tens of nanometers range. A first pp layer was deposited onto substrates using n-heptylamine (HA) to a thickness of 20 nm. Carboxy-thiolated gold nanoparticles were electrostatically bound onto the surface amine groups of the n-heptylamine plasma polymer (HApp) layer. A second HApp layer was then coated to various thicknesses onto the nanoparticle/HApp surface. The template particles embedded thus in-between the two HApp layers were then dissolved using aqueous KCN solution; monitoring of the plasmon resonance band of the gold nanoparticles enabled verification of template stripping and measurement of the kinetics of stripping. AFM topography images showed little change on extraction of the template nanoparticles, indicating that the plasma polymer layer maintained structural integrity upon template extraction and subsequent drying, and thereby prevented collapse of the empty nanocavities. The concept of template stripping to generate controlled size free volume in thin plasma polymer layers is thus shown to produce robust structures.

  5. Electrochemical post-functionalization of conducting polymers.

    PubMed

    Inagi, Shinsuke; Fuchigami, Toshio

    2014-05-01

    This article summarizes recent progress in the post-functionalization of conjugated polymers by electrochemical methods. These electrochemical polymer reactions typically proceed via electrochemical doping of a conjugated polymer film, followed by chemical transformation. Examples include the quantitative oxidative fluorination of polyfluorenes and oxidative halogenation of polythiophenes, as well as the reductive hydrogenation of polyfluorenones. The degree of functionalization, otherwise known as the reaction ratio, can be controlled by varying the charge passed through the polymer, allowing the optoelectronic properties of the conjugated polymers to be tailored. Wireless bipolar electrodes with an in-plane potential distribution are also useful with regard to the electrochemical doping and reaction of conjugated polymers and allow the synthesis of films exhibiting composition gradients. Such bipolar electrochemistry can induce multiple reaction sites during electrochemical polymer reactions.

  6. Increasing the open-circuit voltage in high-performance organic photovoltaic devices through conformational twisting of an indacenodithiophene-based conjugated polymer.

    PubMed

    Chen, Chih-Ping; Hsu, Hsiang-Lin

    2013-10-01

    A fused ladder indacenodithiophene (IDT)-based donor-acceptor (D-A)-type alternating conjugated polymer, PIDTHT-BT, presenting n-hexylthiophene conjugated side chains is prepared. By extending the degree of intramolecular repulsion through the conjugated side chain moieties, an energy level for the highest occupied molecular orbital (HOMO) of -5.46 eV--a value approximately 0.27 eV lower than that of its counterpart PIDTDT-BT--is obtained, subsequently providing a fabricated solar cell with a high open-circuit voltage of approximately 0.947 V. The hole mobility (determined using the space charge-limited current model) in a blend film containing 20 wt% PIDTHT-BT) and 80 wt% [6,6]-phenyl-C71 butyric acid methyl ester (PC71 BM) is 2.2 × 10(-9) m(2) V(-1) s(-1), which is within the range of reasonable values for applications in organic photovoltaics. The power conversion efficiency is 4.5% under simulated solar illumination (AM 1.5G, 100 mW cm(-2)).

  7. Low-band-gap conjugated polymers of dithieno[2,3-b:7,6-b]carbazole and diketopyrrolopyrrole: effect of the alkyl side chain on photovoltaic properties.

    PubMed

    Deng, Yunfeng; Chen, Yagang; Liu, Jian; Liu, Lihui; Tian, Hongkun; Xie, Zhiyuan; Geng, Yanhou; Wang, Fosong

    2013-06-26

    Four donor–acceptor (D–A) conjugated polymers of dithieno[2,3-b;7,6-b]carbazole (DTC) and diketopyrrolopyrrole, which have different alkyls on the nitrogen atom in the DTC unit and are named as P-C8C8, P-C5C5, P-C12, and P-C10, respectively, have been synthesized for studying the effect of the alkyl side chains on the optoelectronic properties of the polymers. All polymers are soluble in various organic solvents and exhibit identical optical band gaps (E(g)(opt)) of ~1.3 eV and highest occupied molecular orbital energy levels of ~−5.1 eV. Organic thin-film transistors and bulk heterojunction polymer solar cells (BHJ PSCs) with phenyl-C(71)-butyric acid methyl ester (PC(71)BM) as the electron-accepting material were fabricated via solution spin-casting. Compared to the polymers substituted by branched alkyl chains, the polymers with straight alkyl chains show higher hole mobility. Of these polymers, P-C10 exhibits the highest field effect mobility up to 0.011 cm(2)/V·s. The alkyl chain on the DTC unit has a strong impact on the film morphology of polymer:PC(71)BM blends. Severe phase separation was found for polymers containing branched alkyl chains, and those with straight alkyl chains formed uniform films featuring fine phase separation. An open-circuit voltage (V(oc)) of 0.72 V, a short-circuit current density (J(sc)) of 13.4 mA/cm(2), a fill factor (FF) of 62%, and a power conversion efficiency (PCE) of 5.9% were demonstrated for BHJ PSCs based on the P-C10:PC(71)BM [1:3 (w/w)] blend film.

  8. Nitrogen-containing microporous conjugated polymers via carbazole-based oxidative coupling polymerization: preparation, porosity, and gas uptake.

    PubMed

    Chen, Qi; Liu, De-Peng; Luo, Min; Feng, Li-Juan; Zhao, Yan-Chao; Han, Bao-Hang

    2014-01-29

    Facile preparation of microporous conjugated polycarbazoles via carbazole-based oxidative coupling polymerization is reported. The process to form the polymer network has cost-effective advantages such as using a cheap catalyst, mild reaction conditions, and requiring a single monomer. Because no other functional groups such as halo groups, boric acid, and alkyne are required for coupling polymerization, properties derived from monomers are likely to be fully retained and structures of final polymers are easier to characterize. A series of microporous conjugated polycarbazoles (CPOP-2-7) with permanent porosity are synthesized using versatile carbazolyl-bearing 2D and 3D conjugated core structures with non-planar rigid conformation as building units. The Brunauer-Emmett-Teller specific surface area values for these porous materials vary between 510 and 1430 m(2) g(-1) . The dominant pore sizes of the polymers based on the different building blocks are located between 0.59 and 0.66 nm. Gas (H2 and CO2 ) adsorption isotherms show that CPOP-7 exhibits the best uptake capacity for hydrogen (1.51 wt% at 1.0 bar and 77 K) and carbon dioxide (13.2 wt% at 1.0 bar and 273 K) among the obtained polymers. Furthermore, its high CH4 /N2 and CO2 /N2 adsorption selectivity gives polymer CPOP-7 potential application in gas separation.

  9. Biotin selective polymer nano-films

    PubMed Central

    2014-01-01

    Background The interaction between biotin and avidin is utilized in a wide range of assay and diagnostic systems. A robust material capable of binding biotin should offer scope in the development of reusable assay materials and biosensor recognition elements. Results Biotin-selective thin (3–5 nm) films have been fabricated on hexadecanethiol self assembled monolayer (SAM) coated Au/quartz resonators. The films were prepared based upon a molecular imprinting strategy where N,N'-methylenebisacrylamide and 2-acrylamido-2-methylpropanesulfonic acid were copolymerized and grafted to the SAM-coated surface in the presence of biotin methyl ester using photoinitiation with physisorbed benzophenone. The biotinyl moiety selectivity of the resonators efficiently differentiated biotinylated peptidic or carbohydrate structures from their native counterparts. Conclusions Molecularly imprinted ultra thin films can be used for the selective recognition of biotinylated structures in a quartz crystal microbalance sensing platform. These films are stable for periods of at least a month. This strategy should prove of interest for use in other sensing and assay systems. PMID:24655809

  10. Inorganic-polymer-derived dielectric films

    DOEpatents

    Brinker, C.J.; Keefer, K.D.; Lenahan, P.M.

    1985-02-25

    A method is disclosed for coating a substrate with a thin film of a predetermined porosity. The method comprises: depositing the thin film on the substrate from a non-gelled solution comprising at least one metal alkoxide of a polymeric network forming cation, water, an alcohol compatible with the hydrolysis and the polymerization of the metal alkoxide, and an acid or a base; prior to said depositing step, controlling the porosity and structure of said coating for a given composition of said solution exclusive of the acid or base component and the water component, by adjusting each of the water content, the pH, the temperature and the time of standing of said solution, increasing/descreasing the water content or the pH to increase/decrease the pore size of said coating, and increasing/decreasing the temperature or time of standing of said solution to increase/decrease the pore size of said coating; and curing said deposited film at a temperature effective for curing whereby there is obtained a thin film coating of a predetermined porosity on the substrate.

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

    PubMed

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

    2015-04-01

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

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

    PubMed

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

    2016-04-06

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

  13. Threshold-like complexation of conjugated polymers with small molecule acceptors in solution within the neighbor-effect model.

    PubMed

    Sosorev, Andrey Yu; Parashchuk, Olga D; Zapunidi, Sergey A; Kashtanov, Grigoriy S; Golovnin, Ilya V; Kommanaboyina, Srikanth; Perepichka, Igor F; Paraschuk, Dmitry Yu

    2016-02-14

    In some donor-acceptor blends based on conjugated polymers, a pronounced charge-transfer complex (CTC) forms in the electronic ground state. In contrast to small-molecule donor-acceptor blends, the CTC concentration in polymer:acceptor solution can increase with the acceptor content in a threshold-like way. This threshold-like behavior was earlier attributed to the neighbor effect (NE) in the polymer complexation, i.e., next CTCs are preferentially formed near the existing ones; however, the NE origin is unknown. To address the factors affecting the NE, we record the optical absorption data for blends of the most studied conjugated polymers, poly(2-methoxy-5-(2-ethylhexyloxy)-1,4-phenylenevinylene) (MEH-PPV) and poly(3-hexylthiophene) (P3HT), with electron acceptors of fluorene series, 1,8-dinitro-9,10-antraquinone (), and 7,7,8,8-tetracyanoquinodimethane () in different solvents, and then analyze the data within the NE model. We have found that the NE depends on the polymer and acceptor molecular skeletons and solvent, while it does not depend on the acceptor electron affinity and polymer concentration. We conclude that the NE operates within a single macromolecule and stems from planarization of the polymer chain involved in the CTC with an acceptor molecule; as a result, the probability of further complexation with the next acceptor molecules at the adjacent repeat units increases. The steric and electronic microscopic mechanisms of NE are discussed.

  14. Synthesis of an end-group functionalized polyethylene glycol-lipid conjugate for preparation of polymer-grafted liposomes.

    PubMed

    Zalipsky, S

    1993-01-01

    Synthesis of a distearoylphosphatidylethanolamine-polyethylene glycol (DSPE-PEG) conjugate, bearing a hydrazide group at the unattached end of the polymer chain, was achieved using a new heterobifunctional polymeric reagent. The heterobifunctional PEG derivative carrying on one end a reactive succinimidyl carbonate (SC) group and at the other terminal a tert-butyloxycarbonyl (Boc) protected hydrazide group was prepared by an efficient four step process from readily available PEG-2000. The SC-end group of the polymer reacted readily with the amino group of DSPE forming a stable urethane attachment between lipid and PEG. Acidolytic removal of the Boc group yielded a hydrazide-PEG-lipid conjugate suitable for preparation of polymer-grafted liposomes. Taking advantage of the well-documented chemical versatility of hydrazide groups, various biologically relevant ligands can be linked to this type of functionalized liposomes.

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

    PubMed Central

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

    2013-01-01

    The development of efficient organic light-emitting diodes (OLED) and organic photovoltaic cells requires control over the dynamics of spin sensitive excitations. Embedding heavy metal atoms in π-conjugated polymer chains enhances the spin-orbit coupling (SOC), and thus facilitates intersystem crossing (ISC) from the singlet to triplet manifolds. Here we use various nonlinear optical spectroscopies such as two-photon absorption and electroabsorption in conjunction with electronic structure calculations, for studying the energies, emission bands and ultrafast dynamics of spin photoexcitations in two newly synthesized π-conjugated polymers that contain intrachain platinum (Pt) atoms separated by one (Pt-1) or three (Pt-3) organic spacer units. The controllable SOC in these polymers leads to a record ISC time of <~1 ps in Pt-1 and ~6 ps in Pt-3. The tunable ultrafast ISC rate modulates the intensity ratio of the phosphorescence and fluorescence emission bands, with potential applications for white OLEDs. PMID:24030602

  16. Well-Defined Protein/Peptide-Polymer Conjugates by Aqueous Cu-LRP: Synthesis and Controlled Self-Assembly.

    PubMed

    Zhang, Qiang; Li, Muxiu; Zhu, Chongyu; Nurumbetov, Gabit; Li, Zaidong; Wilson, Paul; Kempe, Kristian; Haddleton, David M

    2015-07-29

    The synthesis of well-defined protein/peptide-polymer conjugates with interesting self-assembly behavior via single electron transfer living radical polymerization in water is described. A range of protein/peptides with different physical and chemical properties have been modified to macroinitiators and optimized polymerization conditions ensure successful polymerization from soluble, insoluble, and dispersed protein/peptide molecules or protein aggregates. This powerful strategy tolerates a range of functional monomers and mediates efficient homo or block copolymerization to generate hydrophilic polymers with controlled molecular weight (MW) and narrow MW distribution. The polymerizations from bovine insulin macroinitiators follow surface-initiated "grafting from" polymerization mechanism and may involve a series of self-assembly and disassembly processes. Synthesized insulin-polymer conjugates form spheres in water, and the self-assembly behavior could be controlled via thermal control, carbohydrate-protein interaction, and protein denaturation.

  17. Facile Control of a Wide Range of Regioregularity: Significant Influence on Mechanical and Electrical Properties of Conjugated Polymers

    NASA Astrophysics Data System (ADS)

    Kim, Jin-Seong; Kim, Jae-Han; Lee, Wonho; Yu, Hojeong; Kim, Hyeong Jun; Song, Inho; Oh, Joon Hak; Kim, Taek-Soo; Kim, Bumjoon; Postech Collaboration

    2015-03-01

    While regioregularity (RR) has been known to have a strong influence on inherent properties of conjugated polymer, systematic study of RR has been limited due to the lack of synthetic methodology. Herein, we prepared a series of poly(3-hexypthiophenes) (P3HTs) having a wide range of RR from 64 to 98% by the modified Grignard metathesis method that utilizes the dimer moiety. We observed that the RR determines crystalline behavior, mechanical and electrical properties of P3HT. Although higher RR P3HT had higher hole mobility, its increased degree of crystallinity induced fragile nature of polymers (elongation break <1%). In contrast, lower RR had lower elastic modulus and thereby leading to significant reduction of fragility. Therefore, our finding suggested that the control of RR is critical to regulate the properties of conjugated polymers between electrical performance and mechanical resilience as depending on the purpose of the applications. (i.e flexible portable devices vs high performance panel)

  18. Molecular Dynamics Simulations of Gas Transport in Polymer Films

    NASA Astrophysics Data System (ADS)

    Whitley, David; Butler, Simon; Adolf, David

    2010-03-01

    Parallel molecular dynamics simulations have been carried out to determine the permeability of O2 and N2 through polyethylene terephthalate, polypropylene and cis(1-4) polybutadiene. The permeability of both mixed and unmixed gas penetrants is studied within films of these well known gas barrier polymers. Results are obtained either through the solubility and diffusion (i.e. P=D*S) or via the permeability directly. Encouraging results are obtained. Additional analysis focuses on ``unmixed/mixed gas'' intracomparisons of the simulated permeability data in addition to corresponding penetrant and host polymer local dynamics.

  19. Manufacturing polymer thin films in a micro-gravity environment

    NASA Technical Reports Server (NTRS)

    Vera, Ivan

    1987-01-01

    This project represents Venezuela's first scientific experiment in space. The apparatus for the automatic casting of two polymer thin films will be contained in NASA's Payload No. G-559 of the Get Away Special program for a future orbital space flight in the U.S. Space Shuttle. Semi-permeable polymer membranes have important applications in a variety of fields, such as medicine, energy, and pharmaceuticals and in general fluid separation processes, such as reverse osmosis, ultrafiltration, and electrodialysis. The casting of semi-permeable membranes in space will help to identify the roles of convection in determining the structure of these membranes.

  20. Dynamic Mechanical Characterization of Thin Film Polymer Nanocomposites

    NASA Technical Reports Server (NTRS)

    Herring, Helen M.; Gates, Thomas S. (Technical Monitor)

    2003-01-01

    Many new materials are being produced for aerospace applications with the objective of maximizing certain ideal properties without sacrificing others. Polymer composites in various forms and configurations are being developed in an effort to provide lighter weight construction and better thermal and electrical properties and still maintain adequate strength and stability. To this end, thin film polymer nanocomposites, synthesized for the purpose of influencing electrical conductivity using metal oxide particles as filler without incurring losses in mechanical properties, were examined to determine elastic modulus and degree of dispersion of particles. The effects of various metal oxides on these properties will be discussed.