Arctic Oil Spill Response Guide for the Alaskan Beaufort Sea

DTIC Science & Technology

1988-03-01

metallic materials coated with a high temperature polymer (Figure 4.3.8.1). Buoyancy is provided by a series of stainless steel floats. This boom is...S I, / / Fence No Sk Irt - (Ouring Test I) ) 314* metal Bands I Between Therw* Iiss 3/115 Wire Cable Layer and Chain-Link Fence (2 Sands/Can) Metal ...held adjacent to flotation cans with steel bands. Flotation: 5-gal metal cans, 18 In. apart and attached to 3/16-in. cable. Skirt: None used in this

Thermally induced texture flip in semiconducting polymer stabilized by epitaxial relationship

NASA Astrophysics Data System (ADS)

O'Hara, Kathryn A.; Pokuri, Balaji S. S.; Takacs, Christopher J.; Beaujuge, Pierre M.; Ganapathysubramanian, Baskar; Chabinyc, Michael L.

The morphology of semiconducting polymer films has a large effect on the charge transport properties. Charges can move easily along the conjugated backbone and in the pi-pi stacking direction. However, transport through the film is determined by the connectivity between domains, which is not well understood. We previously observed quadrites in the polymer, PSBTBT, and proposed that the preferential overlap between lamellae may improve connectivity and provide an additional conduction pathway. Now, the presence of quadrites is revealed in another successful donor polymer, PBDTTPD, using high resolution transmission electron microscopy (HRTEM). A study of how side-chain substitution affects the epitaxial crossing is conducted by examining several PBDTTPD derivatives. The stability of the film texture with annealing is also examined as a function of quadrite formation. It has been shown that heating some semicrystalline polymers above the melting temperature and slow cooling can flip the lamellar texture from face-on to edge-on. We hypothesize that the orientation of lamellar crystallites in PBDTTPD films is stabilized by the epitaxial overlap between adjacent crystalline domains. This may have important implications for the electronic transport properties.

A phenomenological molecular model for yielding and brittle-ductile transition of polymer glasses

NASA Astrophysics Data System (ADS)

Wang, Shi-Qing; Cheng, Shiwang; Lin, Panpan; Li, Xiaoxiao

2014-09-01

This work formulates, at a molecular level, a phenomenological theoretical description of the brittle-ductile transition (BDT) in tensile extension, exhibited by all polymeric glasses of high molecular weight (MW). The starting point is our perception of a polymer glass (under large deformation) as a structural hybrid, consisting of a primary structure due to the van der Waals bonding and a chain network whose junctions are made of pairs of hairpins and function like chemical crosslinks due to the intermolecular uncrossability. During extension, load-bearing strands (LBSs) emerge between the junctions in the affinely strained chain network. Above the BDT, i.e., at "warmer" temperatures where the glass is less vitreous, the influence of the chain network reaches out everywhere by activating all segments populated transversely between LBSs, starting from those adjacent to LBSs. It is the chain network that drives the primary structure to undergo yielding and plastic flow. Below the BDT, the glassy state is too vitreous to yield before the chain network suffers a structural breakdown. Thus, brittle failure becomes inevitable. For any given polymer glass of high MW, there is one temperature TBD or a very narrow range of temperature where the yielding of the glass barely takes place as the chain network also reaches the point of a structural failure. This is the point of the BDT. A theoretical analysis of the available experimental data reveals that (a) chain pullout occurs at the BDT when the chain tension builds up to reach a critical value fcp during tensile extension; (b) the limiting value of fcp, extrapolated to far below the glass transition temperature Tg, is of a universal magnitude around 0.2-0.3 nN, for all eight polymers examined in this work; (c) pressurization, which is known [K. Matsushige, S. V. Radcliffe, and E. Baer, J. Appl. Polym. Sci. 20, 1853 (1976)] to make brittle polystyrene (PS) and poly(methyl methacrylate) (PMMA) ductile at room temperature, can cause fcp to rise above its ambient value, reaching 0.6 nN at 0.8 kbar. Our theoretical description identifies the areal density ψ of LBSs in the chain network as the key structural parameter to depict the characteristics of the BDT for all polymer glasses made of flexible (Gaussian) linear chains. In particular, it explains the surprising linear correlation between the tensile stress σBD at the BDT and ψ. Moreover, the theoretical picture elucidates how and why each of the following four factors can change the coordinates (σBD, TBD) of the BDT: (i) mechanical "rejuvenation" (i.e., large deformation below Tg), (ii) physical aging, (iii) melt stretching, and (iv) pressurization. Finally, two methods are put forward to delineate the degree of vitrification among various polymer glasses. First, we plot the distance of the BDT from Tg, i.e., Tg/TBD as a function of ψ to demonstrate that different classes of polymer glasses with varying degree of vitrification show different functional dependence of Tg/TBD on ψ. Second, we plot the tensile yield stress σY as a function Tg/T to show that bisphenol-A polycarbonate (bpA-PC) is less vitreous than PS and PMMA whose σY is considerably higher and shows much stronger dependence on Tg/T than that of bpA-PC.

A phenomenological molecular model for yielding and brittle-ductile transition of polymer glasses.

PubMed

Wang, Shi-Qing; Cheng, Shiwang; Lin, Panpan; Li, Xiaoxiao

2014-09-07

This work formulates, at a molecular level, a phenomenological theoretical description of the brittle-ductile transition (BDT) in tensile extension, exhibited by all polymeric glasses of high molecular weight (MW). The starting point is our perception of a polymer glass (under large deformation) as a structural hybrid, consisting of a primary structure due to the van der Waals bonding and a chain network whose junctions are made of pairs of hairpins and function like chemical crosslinks due to the intermolecular uncrossability. During extension, load-bearing strands (LBSs) emerge between the junctions in the affinely strained chain network. Above the BDT, i.e., at "warmer" temperatures where the glass is less vitreous, the influence of the chain network reaches out everywhere by activating all segments populated transversely between LBSs, starting from those adjacent to LBSs. It is the chain network that drives the primary structure to undergo yielding and plastic flow. Below the BDT, the glassy state is too vitreous to yield before the chain network suffers a structural breakdown. Thus, brittle failure becomes inevitable. For any given polymer glass of high MW, there is one temperature TBD or a very narrow range of temperature where the yielding of the glass barely takes place as the chain network also reaches the point of a structural failure. This is the point of the BDT. A theoretical analysis of the available experimental data reveals that (a) chain pullout occurs at the BDT when the chain tension builds up to reach a critical value f(cp) during tensile extension; (b) the limiting value of f(cp), extrapolated to far below the glass transition temperature T(g), is of a universal magnitude around 0.2-0.3 nN, for all eight polymers examined in this work; (c) pressurization, which is known [K. Matsushige, S. V. Radcliffe, and E. Baer, J. Appl. Polym. Sci. 20, 1853 (1976)] to make brittle polystyrene (PS) and poly(methyl methacrylate) (PMMA) ductile at room temperature, can cause f(cp) to rise above its ambient value, reaching 0.6 nN at 0.8 kbar. Our theoretical description identifies the areal density ψ of LBSs in the chain network as the key structural parameter to depict the characteristics of the BDT for all polymer glasses made of flexible (Gaussian) linear chains. In particular, it explains the surprising linear correlation between the tensile stress σ(BD) at the BDT and ψ. Moreover, the theoretical picture elucidates how and why each of the following four factors can change the coordinates (σ(BD), T(BD)) of the BDT: (i) mechanical "rejuvenation" (i.e., large deformation below T(g)), (ii) physical aging, (iii) melt stretching, and (iv) pressurization. Finally, two methods are put forward to delineate the degree of vitrification among various polymer glasses. First, we plot the distance of the BDT from T(g), i.e., T(g)/T(BD) as a function of ψ to demonstrate that different classes of polymer glasses with varying degree of vitrification show different functional dependence of T(g)/T(BD) on ψ. Second, we plot the tensile yield stress σ(Y) as a function T(g)/T to show that bisphenol-A polycarbonate (bpA-PC) is less vitreous than PS and PMMA whose σ(Y) is considerably higher and shows much stronger dependence on T(g)/T than that of bpA-PC.

Interpenetrating and non-interpenetrating 3-dimensional coordination polymer frameworks from multiple building blocks

NASA Astrophysics Data System (ADS)

Bradshaw, Darren; Rosseinsky, Matthew J.

2005-12-01

Reaction of Co(NO3)2ṡ6H2O with the multidentate ligands benzene-1,3,5-tricarboxylate (btc) and the flexible bipyridyl ligand 1,2-bis(4-pyridyl)ethane (bpe) affords the 3-dimensional coordination polymers [Co3(btc)2(bpe)3(eg)2]ṡ(guests) 1, where eg = ethylene glycol, and [Co2(Hbtc)2(bpe)2]ṡ(bpe) 2. Both phases are comprised of infinite metal-carboxylate dimer chains, linked into 2-dimensional sheets by the bpe ligands. These sheets are further linked to adjacent sheets through covalent interactions, 1, or through hydrogen-bonding interactions, 2, to yield the 3-dimensional structures. Phase 1 exhibits solvent filled 1-dimensional pores, whereas 2 is triply-interpenetrated to form a dense solid array.

Fibroblast Growth Factor-based Signaling through Synthetic Heparan Sulfate Blocks Copolymers Studied Using High Cell Density Three-dimensional Cell Printing*

PubMed Central

Sterner, Eric; Masuko, Sayaka; Li, Guoyun; Li, Lingyun; Green, Dixy E.; Otto, Nigel J.; Xu, Yongmei; DeAngelis, Paul L.; Liu, Jian; Dordick, Jonathan S.; Linhardt, Robert J.

2014-01-01

Four well-defined heparan sulfate (HS) block copolymers containing S-domains (high sulfo group content) placed adjacent to N-domains (low sulfo group content) were chemoenzymatically synthesized and characterized. The domain lengths in these HS block co-polymers were ∼40 saccharide units. Microtiter 96-well and three-dimensional cell-based microarray assays utilizing murine immortalized bone marrow (BaF3) cells were developed to evaluate the activity of these HS block co-polymers. Each recombinant BaF3 cell line expresses only a single type of fibroblast growth factor receptor (FGFR) but produces neither HS nor fibroblast growth factors (FGFs). In the presence of different FGFs, BaF3 cell proliferation showed clear differences for the four HS block co-polymers examined. These data were used to examine the two proposed signaling models, the symmetric FGF2-HS2-FGFR2 ternary complex model and the asymmetric FGF2-HS1-FGFR2 ternary complex model. In the symmetric FGF2-HS2-FGFR2 model, two acidic HS chains bind in a basic canyon located on the top face of the FGF2-FGFR2 protein complex. In this model the S-domains at the non-reducing ends of the two HS proteoglycan chains are proposed to interact with the FGF2-FGFR2 protein complex. In contrast, in the asymmetric FGF2-HS1-FGFR2 model, a single HS chain interacts with the FGF2-FGFR2 protein complex through a single S-domain that can be located at any position within an HS chain. Our data comparing a series of synthetically prepared HS block copolymers support a preference for the symmetric FGF2-HS2-FGFR2 ternary complex model. PMID:24563485

Structural variability in Cu(I) and Ag(I) coordination polymers with a flexible dithione ligand: Synthesis, crystal structure, microbiological and theoretical studies

NASA Astrophysics Data System (ADS)

Beheshti, Azizolla; Nozarian, Kimia; Babadi, Susan Soleymani; Noorizadeh, Siamak; Motamedi, Hossein; Mayer, Peter; Bruno, Giuseppe; Rudbari, Hadi Amiri

2017-05-01

Two new compounds namely [Cu(SCN)(μ-L)]n (1) and {[Ag (μ2-L)](ClO4)}n (2) have been synthesized at room temperature by one-pot reactions between the 1,1-(1,4-butanediyl)bis(1,3-dihydro-3-methyl-1H-imidazole- 2-thione) (L) and appropriate copper(I) and silver(I) salts. These polymers have been characterized by single crystal X-ray diffraction, XRPD, TGA, elemental analysis, infrared spectroscopy, antibacterial activity and scanning probe microscopy studies. In the crystal structure of 1, copper atoms have a distorted trigonal planar geometry with a CuS2N coordination environment. Each of the ligands in the structure of 1 acting as a bidentate S-bridging ligand to form a 1D chain structure. Additionally, the adjacent 1D chains are interconnected by the intermolecular C-H…S interactions to create a 2D network structure. In contrast to 1, in the cationic 3D structure of 2 each of the silver atoms exhibits an AgS4 tetrahedral geometry with 4-membered Ag2S2 rings. In the structure of 2, the flexible ligand adopts two different conformations; gauche-anti-gauche and anti-anti-anti. The antibacterial studies of these polymers showed that polymer 2 is more potent antibacterial agent than 1. Scanning probe microscopy (SPM) study of the treated bacteria was carried out to investigate the structural changes cause by the interactions between the polymers and target bacteria. Theoretical study of polymer 1 investigated by the DFT calculations indicates that observed transitions at 266 nm and 302 nm in the UV-vis spectrum could be attributed to the π→π* and MLCT transitions, respectively.

Polymer Chain Conformation and Dynamical Confinement in a Model One-Component Nanocomposite

NASA Astrophysics Data System (ADS)

Mark, C.; Holderer, O.; Allgaier, J.; Hübner, E.; Pyckhout-Hintzen, W.; Zamponi, M.; Radulescu, A.; Feoktystov, A.; Monkenbusch, M.; Jalarvo, N.; Richter, D.

2017-07-01

We report a neutron-scattering investigation on the structure and dynamics of a single-component nanocomposite based on SiO2 particles that were grafted with polyisoprene chains at the entanglement limit. By skillful labeling, we access both the monomer density in the corona as well as the conformation of the grafted chains. While the corona profile follows a r-1 power law, the conformation of a grafted chain is identical to that of a chain in a reference melt, implying a high mutual penetration of the coronas from different particles. The brush crowding leads to topological confinement of the chain dynamics: (i) At local scales, the segmental dynamics is unchanged compared to the reference melt, while (ii) at the scale of the chain, the dynamics appears to be slowed down; (iii) by performing a mode analysis in terms of end-fixed Rouse chains, the slower dynamics is tracked to topological confinement within the cone spanned by the adjacent grafts; (iv) by adding 50% matrix chains, the topological confinement sensed by the grafted chain is lifted partially and the apparent chain motion is accelerated. We observe a crossover from pure Rouse motion at short times to topological confined motion beyond the time when the segmental mean squared displacement has reached the distance to the next graft.

Effect of Chain Conformation on the Single-Molecule Melting Force in Polymer Single Crystals: Steered Molecular Dynamics Simulations Study.

PubMed

Feng, Wei; Wang, Zhigang; Zhang, Wenke

2017-02-28

Understanding the relationship between polymer chain conformation as well as the chain composition within the single crystal and the mechanical properties of the corresponding single polymer chain will facilitate the rational design of high performance polymer materials. Here three model systems of polymer single crystals, namely poly(ethylene oxide) (PEO), polyethylene (PE), and nylon-66 (PA66) have been chosen to study the effects of chain conformation, helical (PEO) versus planar zigzag conformation (PE, PA66), and chain composition (PE versus PA66) on the mechanical properties of a single polymer chain. To do that, steered molecular dynamics simulations were performed on those polymer single crystals by pulling individual polymer chains out of the crystals. Our results show that the patterns of force-extension curve as well as the chain moving mode are closely related to the conformation of the polymer chain in the single crystal. In addition, hydrogen bonds can enhance greatly the force required to stretch the polymer chain out of the single crystal. The dynamic breaking and reformation of multivalent hydrogen bonds have been observed for the first time in PA66 at the single molecule level.

Synthesis of poly(benzothiadiazole-co-dithienobenzodithiophenes) and effect of thiophene insertion for high-performance polymer solar cells.

PubMed

Yun, Hui-Jun; Lee, Yun-Ji; Yoo, Seung-Jin; Chung, Dae Sung; Kim, Yun-Hi; Kwon, Soon-Ki

2013-09-23

We describe herein the synthesis of novel donor-acceptor conjugated polymers with dithienobenzodithiophenes (DTBDT) as the electron donor and 2,1,3-benzothiadiazole as the electron acceptor for high-performance organic photovoltaics (OPVs). We studied the effects of strategically inserting thiophene into the DTBDT as a substituent on the skeletal structure on the opto-electronic performances of fabricated devices. From UV/Vis absorption, electrochemical, and field-effect transistor analyses, we found that the thiophene-containing DTBDT derivative can substantially increase the orbital overlap area between adjacent conjugated chains and thus dramatically enhance charge-carrier mobility up to 0.55 cm(2)  V(-1)  s(-1). The outstanding charge-transport characteristics of this polymer allowed the realization of high-performance organic solar cells with a power conversion efficiency (PCE) of 5.1 %. Detailed studies on the morphological factors that enable the maximum PCE of the polymer solar cells are discussed along with a hole/electron mobility analysis based on the space-charge-limited current model. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Multilayered composite proton exchange membrane and a process for manufacturing the same

DOEpatents

Santurri, Pasco R; Duvall, James H; Katona, Denise M; Mausar, Joseph T; Decker, Berryinne

2015-05-05

A multilayered membrane for use with fuel cells and related applications. The multilayered membrane includes a carrier film, at least one layer of an undoped conductive polymer electrolyte material applied onto the carrier film, and at least one layer of a conductive polymer electrolyte material applied onto the adjacent layer of polymer electrolyte material. Each layer of conductive polymer electrolyte material is doped with a plurality of nanoparticles. Each layer of undoped electrolyte material and doped electrolyte material may be applied in an alternating configuration, or alternatively, adjacent layers of doped conductive polymer electrolyte material is employed. The process for producing a multilayered composite membrane includes providing a carrier substrate and solution casting a layer of undoped conductive polymer electrolyte material and a layer of conductive polymer electrolyte material doped with nanoparticles in an alternating arrangement or in an arrangement where doped layers are adjacent to one another.

Semi-flexible polymer engendered aggregation/dispersion of fullerene (C60) nano-particles: An atomistic investigation

NASA Astrophysics Data System (ADS)

Kumar, Sunil; Pattanayek, Sudip K.

2018-06-01

Semi flexible polymer chain has been modeled by choosing various values of persistent length (stiffness). As the polymer chain stiffness increases, the shape of polymer chain changes from globule to extended cigar to toroid like structure during cooling from a high temperature. The aggregation of fullerene nano-particles is found to depend on the morphology of polymer chain. To maximize, the number of polymer bead-nanoparticle contacts, all nano-particle have positioned inside the polymer globule. To minimize, the energy penalty, due to bending of the polymer chain, all nano-particle have positioned on the surface of the polymer's cigar and toroid morphology.

Synthesis, Amphiphilic Property and Thermal Stability of Novel Main-chain Poly(o-carborane-benzoxazines)

NASA Astrophysics Data System (ADS)

Yang, Xiaoxue; Han, Guo; Yang, Zhen; Zhang, Xiaoa; Jiang, Shengling; Lyu, Yafei

2017-10-01

Five poly(o-carborane-benzoxazines) were synthesized via Mannich reaction of o-carborane bisphenol, paraformaldehyde, and diamine, and their structures were well characterized. Light transmission and 1H NMR in D2O confirmed that poly(o-carborane-benzoxazines) with PEG segments showed excellent water solubility and amphiphilic property. TGA analyses were conducted under nitrogen and air, and the results showed that the polymers own high initial decomposition temperatures owing to the shielding effect of carborane moiety on its adjacent aromatic structures. Besides, poly(o-carborane-benzoxazines) own high char yield at elevated temperatures, for the boron atom could combine with oxygen from the polymer structure or/and the air and be oxidized to form boron oxide, and thus the polymer weight is retained to a large extent. PEG segments had an adverse effect on the initial decomposition and char yield, and thus their concentration should be adjusted to control the polymer’s thermal stability.

The effect of polymer architecture on the interdiffusion in thin polymer films

NASA Astrophysics Data System (ADS)

Caglayan, Ayse; Yuan, Guangcui; Satija, Sushil K.; Uhrig, David; Hong, Kunlun; Akgun, Bulent

Branched polymer chains have been traditionally used in industrial applications as additives. Recently they have found applications in electrochromic displays, lithography, biomedical coatings and targeting multidrug resistant bacteria. In some of these applications where they are confined in thin layers, it is important to understand the relation between the mobility and polymer chain architecture to optimize the processing conditions. Earlier interdiffusion measurements on linear and cyclic polymer chains demonstrated the key role of chain architecture on mobility. We have determined the vertical diffusion coefficients of the star polystyrene chains in thin films as a function of number of polymer arms, molecular weight per arm, and film thickness using neutron reflectivity (NR) and compare our results with linear chains of identical total molecular weight. Bilayer samples of 4-arm and 8-arm protonated polystyrenes (hPS) and deuterated polystyrenes (dPS) were used to elucidate the effect of polymer chain architecture on polymer diffusion. NR measurements indicate that the mobility of polymer chains in thin films get faster as the number of polymer arms increases and the arm molecular weight decreases. Both star polymers showed faster interdiffusion compared to their linear analog. Diffusion coefficient of branched PS chains has a weak dependence on the film thickness.

Competition of the connectivity with the local and the global order in polymer melts and crystals

NASA Astrophysics Data System (ADS)

Bernini, S.; Puosi, F.; Barucco, M.; Leporini, D.

2013-11-01

The competition between the connectivity and the local or global order in model fully flexible chain molecules is investigated by molecular-dynamics simulations. States with both missing (melts) and high (crystal) global order are considered. Local order is characterized within the first coordination shell (FCS) of a tagged monomer and found to be lower than in atomic systems in both melt and crystal. The role played by the bonds linking the tagged monomer to FCS monomers (radial bonds), and the bonds linking two FCS monomers (shell bonds) is investigated. The detailed analysis in terms of Steinhardt's orientation order parameters Ql (l = 2 - 10) reveals that increasing the number of shell bonds decreases the FCS order in both melt and crystal. Differently, the FCS arrangements organize the radial bonds. Even if the molecular chains are fully flexible, the distribution of the angle formed by adjacent radial bonds exhibits sharp contributions at the characteristic angles θ ≈ 70°, 122°, 180°. The fractions of adjacent radial bonds with θ ≈ 122°, 180° are enhanced by the global order of the crystal, whereas the fraction with 70° ≲ θ ≲ 110° is nearly unaffected by the crystallization. Kink defects, i.e., large lateral displacements of the chains, are evidenced in the crystalline state.

Effects of Alkylthio and Alkoxy Side Chains in Polymer Donor Materials for Organic Solar Cells.

PubMed

Cui, Chaohua; Wong, Wai-Yeung

2016-02-01

Side chains play a considerable role not only in improving the solubility of polymers for solution-processed device fabrication, but also in affecting the molecular packing, electron affinity and thus the device performance. In particular, electron-donating side chains show unique properties when employed to tune the electronic character of conjugated polymers in many cases. Therefore, rational electron-donating side chain engineering can improve the photovoltaic properties of the resulting polymer donors to some extent. Here, a survey of some representative examples which use electron-donating alkylthio and alkoxy side chains in conjugated organic polymers for polymer solar cell applications will be presented. It is envisioned that an analysis of the effect of such electron-donating side chains in polymer donors would contribute to a better understanding of this kind of side chain behavior in solution-processed conjugated organic polymers for polymer solar cells. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Facile synthesis of 2D Zn(II) coordination polymer and its crystal structure, selective removal of methylene blue and molecular simulations

NASA Astrophysics Data System (ADS)

Sezer, Güneş Günay; Yeşilel, Okan Zafer; Şahin, Onur; Arslanoğlu, Hasan; Erucar, İlknur

2017-09-01

A new coordination polymer {[Zn(μ3-ppda)(H2O)(μ-bpa)Zn(μ-ppda)(μ-bpa)]·4H2O}n (1) (ppda = 1,4-phenylenediacetate, bpa = 1,2-bis(4-pyridyl)ethane) has been synthesized by microwave-assisted reaction and characterized by elemental analysis, IR spectroscopy, single-crystal and powder X-ray diffractions. The asymmetric unit of 1 consists of two Zn(II) ions, two bpa ligands, two ppda ligands, one coordinated and four non-coordinated water molecules. In 1, ppda2- anions are linked the adjacent Zn(II) centers to generate 1D double-stranded chains. These chains are connected into 2D sheets by the bridging bpa ligands. Atomically detailed modeling was performed to compute single and binary component adsorption isotherms of H2, CO2, CH4 and N2 in complex 1. Results showed that 1 exhibits a high adsorption selectivity towards CO2 due to its high affinity for CO2. Results of this study will be helpful to guide the microwave-assisted reaction of coordination polymers to design promising adsorbents for gas storage and gas separation applications. The luminescent property of 1 and the selective removal of dyes in 1 have been also discussed. Results showed that 1 can be a potential candidate for luminescence applications and can selectively adsorb methylene blue (MB) dye molecules.

Coordination Polymer of M(II)-Pyrazinamide (M = Co, Cd) with Double End-to-End Thiocyanate Bridge

NASA Astrophysics Data System (ADS)

Ponco Prananto, Yuniar

2018-01-01

Pyrazinamide (pza, C4N2H3-CONH2) is a good ligand for coordination polymer. Their transition metal complexes are known to have antibacterial activities, magnetic properties, etc. Coordination polymers of M(II)-pyrazinamide with thiocyanate (M = Co (a), Cd (b)), prepared using bench-top layering technique with M(II):pza:SCN ratio of 1:2:2, is successfully crystallised at room temperature. Single crystal XRD was used to determine the crystal structure. Infrared and melting point determination were also performed. Crystal structure of both complexes, solved in Triclinic P-1, show that each octahedral metal centre is connected to two adjacent metal centres by double end-to-end thiocyanate bridge forming a 1D polymeric structure with M···M distances of 5.524 Å (in a) and 5.887 Å (in b). Two monodentate pyrazinamide ligands occupy the rest of the coordination sites on the metal centre in a trans relationship. Only in complex a, one lattice pyrazinamide molecule is involved in the asymmetric unit. Crystal packing of both a and b are also displaying non-covalent networks as a result of hydrogen-bonding involving the pyrazine ring, amide and carbonyl groups between adjacent chains and π···π interactions (only occurred in a). In addition, the observed melting points of both a and b are relatively close to each other (around 180°C), and ATR-IR spectra support the presence of the bridging thiocyanate and terminal pyrazinamide.

Tuning the thermal conductivity of solar cell polymers through side chain engineering.

PubMed

Guo, Zhi; Lee, Doyun; Liu, Yi; Sun, Fangyuan; Sliwinski, Anna; Gao, Haifeng; Burns, Peter C; Huang, Libai; Luo, Tengfei

2014-05-07

Thermal transport is critical to the performance and reliability of polymer-based energy devices, ranging from solar cells to thermoelectrics. This work shows that the thermal conductivity of a low band gap conjugated polymer, poly(4,8-bis-alkyloxybenzo[1,2-b:4,5-b']dithiophene-2,6-diyl-alt-(alkylthieno[3,4-b]thiophene-2-carboxylate)-2,6-diyl) (PBDTTT), for photovoltaic applications can be actively tuned through side chain engineering. Compared to the original polymer modified with short branched side chains, the engineered polymer using all linear and long side chains shows a 160% increase in thermal conductivity. The thermal conductivity of the polymer exhibits a good correlation with the side chain lengths as well as the crystallinity of the polymer characterized using small-angle X-ray scattering (SAXS) experiments. Molecular dynamics simulations and atomic force microscopy are used to further probe the molecular level local order of different polymers. It is found that the linear side chain modified polymer can facilitate the formation of more ordered structures, as compared to the branched side chain modified ones. The effective medium theory modelling also reveals that the long linear side chain enables a larger heat carrier propagation length and the crystalline phase in the bulk polymer increases the overall thermal conductivity. It is concluded that both the length of the side chains and the induced polymer crystallization are important for thermal transport. These results offer important guidance for actively tuning the thermal conductivity of conjugated polymers through molecular level design.

Critical Casimir effect in a polymer chain in supercritical solvents.

PubMed

Sumi, Tomonari; Imazaki, Nobuyuki; Sekino, Hideo

2009-03-01

Density fluctuation effects on the conformation of a polymer chain in a supercritical solvent were investigated by performing a multiscale simulation based on the density-functional theory. We found (a) a universal swelling of the polymer chain near the critical point, irrespective of whether the polymer chain is solvophilic or solvophobic, and (b) a characteristic collapse of the polymer chain having a strong solvophilicity at a temperature slightly higher than the critical point, where the isothermal compressibility becomes less than the ideal one.

Liquid crystal polymers: evidence of hairpin defects in nematic main chains, comparison with side chain polymers

NASA Astrophysics Data System (ADS)

Li, M. H.; Brûlet, A.; Keller, P.; Cotton, J. P.

1996-09-01

This article describes the conformation of two species of liquid crystalline polymers as revealed by small angle neutron scattering. The results obtained with side chain polymers are recalled. The procedure used to analyze the scattering data of main chains in the nematic phase is reported in this paper. It permits a demonstration of the existence of hairpins. Comparison of both polymer species shows that in the isotropic phase, the two polymers adopt a random coil conformation. In the nematic phase, the conformations are very different; the side chains behave as a melt of penetrable random coils whereas the main chains behave as a nematic phase of non penetrable cylinders.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Luo, Qianqian; Han, Ying; Lin, Hechun, E-mail: hclin@ee.ecnu.edu.cn

One dimensional coordination polymer Gd[(SO{sub 4})(NO{sub 3})(C{sub 2}H{sub 6}SO){sub 2}] (1) is prepared through the mediation of Bronsted acid ionic liquid, which crystallized in the monoclinic space of C2/c. In this polymer, adjacent Gd atoms are linked by two SO{sub 4}{sup 2-} ions to generate a 1-D chain, and all oxygen atoms in SO{sub 4}{sup 2-} groups are connected to three nearest Gd atoms in µ{sup 3}:η{sup 1}:η{sup 1}:η{sup 2} fashion. Gd, S and N from SO{sub 4}{sup 2-} and NO{sub 3}{sup -} are precisely coplanar. The planar is coordinated by a pair of DMSO molecules, which is parallel andmore » linked by hydrogen bonding to form a three-dimensional supramolecular network. Magnetic susceptibility measurement of 1 reveals weak antiferromagnetic interactions between the Gd (III) ions. It exhibits relatively large magneto-caloric effect with –ΔS{sub m}=28.8 J Kg{sup −1} K{sup −1} for ΔH=7 T. - Graphical abstract: Coordination polymer Gd[(SO{sub 4})(NO{sub 3})(C{sub 2}H{sub 6}SO){sub 2}] was obtained mediated by Bronsted acid Ionic Liquid, which presents a 1-D chains collected by SO{sub 4}{sup 2-} groups. Magnetic susceptibility of the polymer reveals weak antiferromagnetic interactions between the Gd(III) ions with the relatively large magneto-caloric effect of –ΔS{sub m}=28.8 J Kg{sup −1} K{sup −1} for ΔH= 7T.« less

Time-Resolved Transient Optical Absorption Study of Bis(terpyridyl)oligothiophenes and Their Metallo-Supramolecular Polymers with Zn(II) Ion Couplers.

PubMed

Rais, David; Menšík, Miroslav; Štenclová-Bláhová, Pavla; Svoboda, Jan; Vohlídal, Jiří; Pfleger, Jiří

2015-06-18

α,ω-Bis(terpyridyl)oligothiophenes spontaneously assemble with Zn(II) ions giving conjugated constitutional dynamic polymers (dynamers) of the metallo-supramolecular class, which potentially might be utilized in optoelectronics. Their photophysical properties, which are of great importance in this field of application, are strongly influenced by the dynamic morphology. It was assessed in this study by using ultrafast pump-probe optical absorption spectroscopy. We identified and characterized relaxation processes running in photoexcited molecules of these oligomers and dynamers and show impacts of disturbed coplanarity of adjacent rings (twisting the thiophene-thiophene and thiophene-terpyridyl bonds by attached hexyl side groups) and Zn(II) ion couplers on these processes. Major effects are seen in the time constants of rotational relaxation, intersystem crossing, and de-excitation lifetimes. The photoexcited states formed on different repeating units within the same dynamer chain do not interact with each other even at very high excitation density. The method is presented that allows determining the equilibrium fraction of unbound oligothiophene species in a dynamer solution, from which otherwise hardly accessible values of the average degree of polymerization of constitutionally dynamic chains in solution can be estimated.

Brownian dynamics simulation of a polymer chain in a solid-state nanopore attached to a molecular stop

NASA Astrophysics Data System (ADS)

Wells, Craig; Hulings, Zachery; Melnikov, Dmitriy; Gracheva, Maria

We study a nanopore inside a silicon dioxide membrane submerged in a KCl solution with a negatively charged polymer chain of varying lengths whose movement is described using Brownian dynamics. The polymer is attached to a molecule with a radius larger than that of the nanopore's which acts as a molecular stop, allowing the chain to thread the nanopore but preventing it from translocating. We found that the polymer chain's variation of movement along the nanopore decreased when increasing applied biases and chain lengths for portions of the chain closest to the molecular stop. The chain displacement within the pore is also compared to a freely translocating polymer where preliminary results show the free polymer having a greater variation in the radial direction. Overall, our preliminary results indicate that the radial direction of the polymer chain is dominated by the confinement in the narrow nanopore with restrictions imposed by the molecular stop and bias playing a lesser role. Understanding the interaction behavior of the polymer chain-stop molecule may lead to methods that decrease movement variation, facilitating an improvement on characterizing and identification of molecules. NSF DMR and CBET Grant No. 1352218.

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.

Flory-type theories of polymer chains under different external stimuli

NASA Astrophysics Data System (ADS)

Budkov, Yu A.; Kiselev, M. G.

2018-01-01

In this Review, we present a critical analysis of various applications of the Flory-type theories to a theoretical description of the conformational behavior of single polymer chains in dilute polymer solutions under a few external stimuli. Different theoretical models of flexible polymer chains in the supercritical fluid are discussed and analysed. Different points of view on the conformational behavior of the polymer chain near the liquid-gas transition critical point of the solvent are presented. A theoretical description of the co-solvent-induced coil-globule transitions within the implicit-solvent-explicit-co-solvent models is discussed. Several explicit-solvent-explicit-co-solvent theoretical models of the coil-to-globule-to-coil transition of the polymer chain in a mixture of good solvents (co-nonsolvency) are analysed and compared with each other. Finally, a new theoretical model of the conformational behavior of the dielectric polymer chain under the external constant electric field in the dilute polymer solution with an explicit account for the many-body dipole correlations is discussed. The polymer chain collapse induced by many-body dipole correlations of monomers in the context of statistical thermodynamics of dielectric polymers is analysed.

Enhancing gelation ability of a dendritic gelator through complexation with a polyelectrolyte.

PubMed

Zhang, Zijian; Yang, Miao; Zhang, Xinjun; Zhang, Lichu; Liu, Bo; Zheng, Ping; Wang, Wei

2009-01-01

A poly(urethane amide) (PUA) dendron with long alkyl chains on its periphery was synthesized and then attached to the backbone of a polyelectrolyte, in which each unit contained a positive charge, by ionizing the carboxyl groups on the apexes of the dendrons to form a dendronized polymer. We found that both the PUA dendron and the dendronized polymer could form organogels in toluene. Interestingly, both the minimum gelation concentration and the gelation time of the dendronized polymer gelator were greatly reduced compared with the dendron alone. Our investigations showed that in the gel phase the intermolecular hydrogen bonding between adjacent dendrons creates similar supramolecular structures in both the dendron and the dendronized polymer gelator, which immobilize solvent molecules by means of interactions between dendrons and solvent molecules. Further studies on the gelation kinetics indicated that the polyelectrolyte backbone plays an important role in prearranging the attached dendritic gelators orderly and quickly into the supramolecular structures through a nucleation-elongation mechanism. Therefore, the gel-forming ability of the dendritic PUA gelator is enhanced by being complexed with the polyelectrolyte. In this work, this positive macromolecular effect is discussed in detail.

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. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Solid polymeric electrolytes for lithium batteries

DOEpatents

Angell, Charles A.; Xu, Wu; Sun, Xiaoguang

2006-03-14

Novel conductive polyanionic polymers and methods for their preparion are provided. The polyanionic polymers comprise repeating units of weakly-coordinating anionic groups chemically linked to polymer chains. The polymer chains in turn comprise repeating spacer groups. Spacer groups can be chosen to be of length and structure to impart desired electrochemical and physical properties to the polymers. Preferred embodiments are prepared from precursor polymers comprising the Lewis acid borate tri-coordinated to a selected ligand and repeating spacer groups to form repeating polymer chain units. These precursor polymers are reacted with a chosen Lewis base to form a polyanionic polymer comprising weakly coordinating anionic groups spaced at chosen intervals along the polymer chain. The polyanionic polymers exhibit high conductivity and physical properties which make them suitable as solid polymeric electrolytes in lithium batteries, especially secondary lithium batteries.

Dependence of Ion Dynamics on the Polymer Chain Length in Poly(ethylene oxide)-Based Polymer Electrolytes.

PubMed

Chattoraj, Joyjit; Knappe, Marisa; Heuer, Andreas

2015-06-04

It is known from experiments that in the polymer electrolyte system, which contains poly(ethylene oxide) chains (PEO), lithium-cations (Li(+)), and bis(trifluoromethanesulfonyl)imide-anions (TFSI(-)), the cation and the anion diffusion and the ionic conductivity exhibit a similar chain-length dependence: with increasing chain length, they start dropping steadily, and later, they saturate to constant values. These results are surprising because Li-cations are strongly correlated with the polymer chains, whereas TFSI-anions do not have such bonding. To understand this phenomenon, we perform molecular dynamics simulations of this system for four different polymer chain lengths. The diffusion results obtained from our simulations display excellent agreement with the experimental data. The cation transport model based on the Rouse dynamics can successfully quantify the Li-diffusion results, which correlates Li diffusion with the polymer center-of-mass motion and the polymer segmental motion. The ionic conductivity as a function of the chain length is then estimated based on the chain-length-dependent ion diffusion, which shows a temperature-dependent deviation for short chain lengths. We argue that in the first regime, counterion correlations modify the conductivity, whereas for the long chains, the system behaves as a strong electrolyte.

Side-Chain Effects on the Thermoelectric Properties of Fluorene-Based Copolymers.

PubMed

Liang, Ansheng; Zhou, Xiaoyan; Zhou, Wenqiao; Wan, Tao; Wang, Luhai; Pan, Chengjun; Wang, Lei

2017-09-01

Three conjugated polymers with alkyl chains of different lengths are designed and synthesized, and their structure-property relationship as organic thermoelectric materials is systematically elucidated. All three polymers show similar photophysical properties, thermal properties, and mechanical properties; however, their thermoelectric performance is influenced by the length of their side chains. The length of the alkyl chain significantly influences the electrical conductivity of the conjugated polymers, and polymers with a short alkyl chain exhibit better conductivity than those with a long alkyl chain. The length of the alkyl chain has little effect on the Seebeck coefficient. Only a slight increase in the Seebeck coefficient is observed with the increasing length of the alkyl chain. The purpose of this study is to provide comprehensive insight into fine-tuning the thermoelectric properties of conjugated polymers as a function of side-chain engineering, thereby providing a novel perspective into the design of high-performance thermoelectric conjugated polymers. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Distribution of Chains in Polymer Brushes Produced by a “Grafting From” Mechanism

DOE PAGES

Martinez, Andre P.; Carrillo, Jan-Michael Y.; Dobrynin, Andrey V.; ...

2016-01-11

The molecular weight and polydispersity of the chains in a polymer brush are critical parameters determining the brush properties. However, the characterization of polymer brushes is hindered by the vanishingly small mass of polymer present in brush layers. In this study, in order to obtain sufficient quantities of polymer for analysis, polymer brushes were grown from high surface area fibrous nylon membranes by ATRP. We synthesized the brushes with varying surface initiator densities, polymerization times, and amounts of sacrificial initiator, then cleaved from the substrate, and analyzed by GPC and NMR. Characterization showed that the surface-grown polymer chains were moremore » polydisperse and had lower average molecular weight compared to solution-grown polymers synthesized concurrently. Furthermore, the molecular weight distribution of the polymer brushes was observed to be bimodal, with a low molecular weight population of chains representing a significant mass fraction of the polymer chains at high surface initiator densities. Moreover, the origin of this low MW polymer fraction is proposed to be the termination of growing chains by recombination during the early stages of polymerization, a mechanism confirmed by molecular dynamics simulations of brush polymerization.« less

A Langevin dynamics simulation study of the tribology of polymer loop brushes.

PubMed

Yin, Fang; Bedrov, Dmitry; Smith, Grant D; Kilbey, S Michael

2007-08-28

The tribology of surfaces modified with doubly bound polymer chains (loops) has been investigated in good solvent conditions using Langevin dynamics simulations. The density profiles, brush interpenetration, chain inclination, normal forces, and shear forces for two flat substrates modified by doubly bound bead-necklace polymers and equivalent singly bound polymers (twice as many polymer chains of 12 the molecular weight of the loop chains) were determined and compared as a function of surface separation, grafting density, and shear velocity. The doubly bound polymer layers showed less interpenetration with decreasing separation than the equivalent singly bound layers. Surprisingly, this difference in interpenetration between doubly bound polymer and singly bound polymer did not result in decreased friction at high shear velocity possibly due to the decreased ability of the doubly bound chains to deform in response to the applied shear. However, at lower shear velocity, where deformation of the chains in the flow direction is less pronounced and the difference in interpenetration is greater between the doubly bound and singly bound chains, some reduction in friction was observed.

Adsorption of poly(ethylene succinate) chain onto graphene nanosheets: A molecular simulation.

PubMed

Kelich, Payam; Asadinezhad, Ahmad

2016-09-01

Understanding the interaction between single polymer chain and graphene nanosheets at local and global length scales is essential for it underlies the mesoscopic properties of polymer nanocomposites. A computational attempt was then performed using atomistic molecular dynamics simulation to gain physical insights into behavior of a model aliphatic polyester, poly(ethylene succinate), single chain near graphene nanosheets, where the effects of the polymer chain length, graphene functionalization, and temperature on conformational properties of the polymer were studied comparatively. Graphene functionalization was carried out through extending the parameters set of an all-atom force field. The results showed a significant conformational transition of the polymer chain from three-dimensional statistical coil, in initial state, to two-dimensional fold, in final state, during adsorption on graphene. The conformational order, overall shape, end-to-end separation statistics, and mobility of the polymer chain were found to be influenced by the graphene functionalization, temperature, and polymer chain length. Furthermore, the polymer chain dynamics mode during adsorption on graphene was observed to transit from normal diffusive to slow subdiffusive mode. The findings from this computational study could shed light on the physics of the early stages of aliphatic polyester chain organization induced by graphene. Copyright © 2016 Elsevier Inc. All rights reserved.

Model systems for single molecule polymer dynamics

PubMed Central

Latinwo, Folarin

2012-01-01

Double stranded DNA (dsDNA) has long served as a model system for single molecule polymer dynamics. However, dsDNA is a semiflexible polymer, and the structural rigidity of the DNA double helix gives rise to local molecular properties and chain dynamics that differ from flexible chains, including synthetic organic polymers. Recently, we developed single stranded DNA (ssDNA) as a new model system for single molecule studies of flexible polymer chains. In this work, we discuss model polymer systems in the context of “ideal” and “real” chain behavior considering thermal blobs, tension blobs, hydrodynamic drag and force–extension relations. In addition, we present monomer aspect ratio as a key parameter describing chain conformation and dynamics, and we derive dynamical scaling relations in terms of this molecular-level parameter. We show that asymmetric Kuhn segments can suppress monomer–monomer interactions, thereby altering global chain dynamics. Finally, we discuss ssDNA in the context of a new model system for single molecule polymer dynamics. Overall, we anticipate that future single polymer studies of flexible chains will reveal new insight into the dynamic behavior of “real” polymers, which will highlight the importance of molecular individualism and the prevalence of non-linear phenomena. PMID:22956980

Introduction to Polymer Chemistry.

ERIC Educational Resources Information Center

Harris, Frank W.

1981-01-01

Reviews the physical and chemical properties of polymers and the two major methods of polymer synthesis: addition (chain, chain-growth, or chain-reaction), and condensation (step-growth or step-reaction) polymerization. (JN)

Brownian dynamics of a protein-polymer chain complex in a solid-state nanopore

NASA Astrophysics Data System (ADS)

Wells, Craig C.; Melnikov, Dmitriy V.; Gracheva, Maria E.

2017-08-01

We study the movement of a polymer attached to a large protein inside a nanopore in a thin silicon dioxide membrane submerged in an electrolyte solution. We use Brownian dynamics to describe the motion of a negatively charged polymer chain of varying lengths attached to a neutral protein modeled as a spherical bead with a radius larger than that of the nanopore, allowing the chain to thread the nanopore but preventing it from translocating. The motion of the protein-polymer complex within the pore is also compared to that of a freely translocating polymer. Our results show that the free polymer's standard deviations in the direction normal to the pore axis is greater than that of the protein-polymer complex. We find that restrictions imposed by the protein, bias, and neighboring chain segments aid in controlling the position of the chain in the pore. Understanding the behavior of the protein-polymer chain complex may lead to methods that improve molecule identification by increasing the resolution of ionic current measurements.

Brownian dynamics of a protein-polymer chain complex in a solid-state nanopore.

PubMed

Wells, Craig C; Melnikov, Dmitriy V; Gracheva, Maria E

2017-08-07

We study the movement of a polymer attached to a large protein inside a nanopore in a thin silicon dioxide membrane submerged in an electrolyte solution. We use Brownian dynamics to describe the motion of a negatively charged polymer chain of varying lengths attached to a neutral protein modeled as a spherical bead with a radius larger than that of the nanopore, allowing the chain to thread the nanopore but preventing it from translocating. The motion of the protein-polymer complex within the pore is also compared to that of a freely translocating polymer. Our results show that the free polymer's standard deviations in the direction normal to the pore axis is greater than that of the protein-polymer complex. We find that restrictions imposed by the protein, bias, and neighboring chain segments aid in controlling the position of the chain in the pore. Understanding the behavior of the protein-polymer chain complex may lead to methods that improve molecule identification by increasing the resolution of ionic current measurements.

Multifunctional Diketopyrrolopyrrole-Based Conjugated Polymers with Perylene Bisimide Side Chains.

PubMed

Li, Cheng; Yu, Changshi; Lai, Wenbin; Liang, Shijie; Jiang, Xudong; Feng, Guitao; Zhang, Jianqi; Xu, Yunhua; Li, Weiwei

2017-11-24

Two conjugated polymers based on diketopyrrolopyrrole (DPP) in the main chain with different content of perylene bisimide (PBI) side chains are developed. The influence of PBI side chain on the photovoltaic performance of these DPP-based conjugated polymers is systematically investigated. This study suggests that the PBI side chains can not only alter the absorption spectrum and energy level but also enhance the crystallinity of conjugated polymers. As a result, such polymers can act as electron donor, electron acceptor, and single-component active layer in organic solar cells. These findings provide a new guideline for the future molecular design of multifunctional conjugated polymers. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Characterization of Hydrophobic Interactions of Polymers with Water and Phospholipid Membranes Using Molecular Dynamics Simulations

NASA Astrophysics Data System (ADS)

Drenscko, Mihaela

Polymers and lipid membranes are both essential soft materials. The structure and hydrophobicity/hydrophilicity of polymers, as well as the solvent they are embedded in, ultimately determines their size and shape. Understating the variation of shape of the polymer as well as its interactions with model biological membranes can assist in understanding the biocompatibility of the polymer itself. Computer simulations, in particular molecular dynamics, can aid in characterization of the interaction of polymers with solvent, as well as polymers with model membranes. In this thesis, molecular dynamics serve to describe polymer interactions with a solvent (water) and with a lipid membrane. To begin with, we characterize the hydrophobic collapse of single polystyrene chains in water using molecular dynamics simulations. Specifically, we calculate the potential of mean force for the collapse of a single polystyrene chain in water using metadynamics, comparing the results between all atomistic with coarse-grained molecular simulation. We next explore the scaling behavior of the collapsed globular shape at the minimum energy configuration, characterized by the radius of gyration, as a function of chain length. The exponent is close to one third, consistent with that predicted for a polymer chain in bad solvent. We also explore the scaling behavior of the Solvent Accessible Surface Area (SASA) as a function of chain length, finding a similar exponent for both all-atomistic and coarse-grained simulations. Furthermore, calculation of the local water density as a function of chain length near the minimum energy configuration suggests that intermediate chain lengths are more likely to form dewetted states, as compared to shorter or longer chain lengths. Next, in order to investigate the molecular interactions between single hydrophobic polymer chains and lipids in biological membranes and at lipid membrane/solvent interface, we perform a series of molecular dynamics simulations of small membranes using all atomistic and coarse-grained methods. The molecular interaction between common polymer chains used in biomedical applications and the cell membrane is unknown. This interaction may affect the biocompatibility of the polymer chains. Molecular dynamics simulations offer an emerging tool to characterize the interaction between common degradable polymer chains used in biomedical applications, such as polycaprolactone, and model cell membranes. We systematically characterize with long-time all-atomistic molecular dynamics simulations the interaction between single polycaprolactone chains of varying chain lengths with a model phospholipid membrane. We find that the length of polymer chain greatly affects the nature of interaction with the membrane, as well as the membrane properties. Furthermore, we next utilize advanced sampling techniques in molecular dynamics to characterize the two-dimensional free energy surface for the interaction of varying polymer chain lengths (short, intermediate, and long) with model cell membranes. We find that the free energy minimum shifts from the membrane-water interface to the hydrophobic core of the phospholipid membrane as a function of chain length. These results can be used to design polymer chain lengths and chemistries to optimize their interaction with cell membranes at the molecular level.

Confined dynamics of grafted polymer chains in solutions of linear polymer

DOE PAGES

Poling-Skutvik, Ryan D.; Olafson, Katy N.; Narayanan, Suresh; ...

2017-09-11

Here, we measure the dynamics of high molecular weight polystyrene grafted to silica nanoparticles dispersed in semidilute solutions of linear polymer. Structurally, the linear free chains do not penetrate the grafted corona but increase the osmotic pressure of the solution, collapsing the grafted polymer and leading to eventual aggregation of the grafted particles at high matrix concentrations. Dynamically, the relaxations of the grafted polymer are controlled by the solvent viscosity according to the Zimm model on short time scales. On longer time scales, the grafted chains are confined by neighboring grafted chains, preventing full relaxation over the experimental time scale.more » Adding free linear polymer to the solution does not affect the initial Zimm relaxations of the grafted polymer but does increase the confinement of the grafted chains. Finally, our results elucidate the physics underlying the slow relaxations of grafted polymer.« less

Confined dynamics of grafted polymer chains in solutions of linear polymer

DOE Office of Scientific and Technical Information (OSTI.GOV)

Poling-Skutvik, Ryan D.; Olafson, Katy N.; Narayanan, Suresh

Here, we measure the dynamics of high molecular weight polystyrene grafted to silica nanoparticles dispersed in semidilute solutions of linear polymer. Structurally, the linear free chains do not penetrate the grafted corona but increase the osmotic pressure of the solution, collapsing the grafted polymer and leading to eventual aggregation of the grafted particles at high matrix concentrations. Dynamically, the relaxations of the grafted polymer are controlled by the solvent viscosity according to the Zimm model on short time scales. On longer time scales, the grafted chains are confined by neighboring grafted chains, preventing full relaxation over the experimental time scale.more » Adding free linear polymer to the solution does not affect the initial Zimm relaxations of the grafted polymer but does increase the confinement of the grafted chains. Finally, our results elucidate the physics underlying the slow relaxations of grafted polymer.« less

Bifunctional Organic Polymeric Catalysts with a Tunable Acid-Base Distance and Framework Flexibility

PubMed Central

Chen, Huanhui; Wang, Yanan; Wang, Qunlong; Li, Junhui; Yang, Shiqi; Zhu, Zhirong

2014-01-01

Acid-base bifunctional organic polymeric catalysts were synthesized with tunable structures. we demonstrated two synthesis approaches for structural fine-tune. In the first case, the framework flexibility was tuned by changing the ratio of rigid blocks to flexible blocks within the polymer framework. In the second case, we precisely adjusted the acid-base distance by distributing basic monomers to be adjacent to acidic monomers, and by changing the chain length of acidic monomers. In a standard test reaction for the aldol condensation of 4-nitrobenzaldehyde with acetone, the catalysts showed good reusability upon recycling and maintained relatively high conversion percentage. PMID:25267260

Reduced viscosity for flagella moving in a solution of long polymer chains

NASA Astrophysics Data System (ADS)

Zhang, Yuchen; Li, Gaojin; Ardekani, Arezoo M.

2018-02-01

The bacterial flagellum thickness is smaller than the radius of gyration of long polymer chain molecules. The flow velocity gradient over the length of polymer chains can be nonuniform and continuum models of polymeric liquids break in this limit. In this work, we use Brownian dynamics simulations to study a rotating helical flagellum in a polymer solution and overcome this limitation. As the polymer size increases, the viscosity experienced by the flagellum asymptotically reduces to the solvent viscosity. The contribution of polymer molecules to the local viscosity in a solution of long polymer chains decreases with the inverse of polymer size to the power 1/2. The difference in viscosity experienced by the bacterial cell body and flagella can predict the nonmonotonic swimming speed of bacteria in polymer solutions.

Stretching of a polymer chain anchored to a surface: the massive field theory approach

NASA Astrophysics Data System (ADS)

Usatenko, Zoryana

2014-09-01

Taking into account the well-known correspondence between the field theoretical φ4 O(n)-vector model in the limit n → 0 and the behaviour of long-flexible polymer chains, the investigation of stretching of an ideal and a real polymer chain with excluded volume interactions in a good solvent anchored to repulsive and inert surfaces is performed. The calculations of the average stretching force which arises when the free end of a polymer chain moves away from a repulsive or inert surface are performed up to one-loop order of the massive field theory approach in fixed space dimensions d = 3. The analysis of the obtained results indicates that the average stretching force for a real polymer chain anchored to a repulsive surface demonstrates different behaviour for the cases \\tilde{z}\\ll1 and \\tilde{z}\\gg1 , where \\tilde{z}=z^\\prime/Rz . Besides, the results obtained in the framework of the massive field theory approach are in good agreement with previous theoretical results for an ideal polymer chain and results of a density functional theory approach for the region of small applied forces when deformation of a polymer chain in the direction of the applied force is not bigger than the linear extension of a polymer chain in this direction. The better agreement between these two methods is observed in the case where the number of monomers increases and the polymer chain becomes longer.

Polymer composites containing nanotubes

NASA Technical Reports Server (NTRS)

Bley, Richard A. (Inventor)

2008-01-01

The present invention relates to polymer composite materials containing carbon nanotubes, particularly to those containing singled-walled nanotubes. The invention provides a polymer composite comprising one or more base polymers, one or more functionalized m-phenylenevinylene-2,5-disubstituted-p-phenylenevinylene polymers and carbon nanotubes. The invention also relates to functionalized m-phenylenevinylene-2,5-disubstituted-p-phenylenevinylene polymers, particularly to m-phenylenevinylene-2,5-disubstituted-p-phenylenevinylene polymers having side chain functionalization, and more particularly to m-phenylenevinylene-2,5-disubstituted-p-phenylenevinylene polymers having olefin side chains and alkyl epoxy side chains. The invention further relates to methods of making polymer composites comprising carbon nanotubes.

On the Interfacial Properties of Polymers/Functionalized Single-Walled Carbon Nanotubes

NASA Astrophysics Data System (ADS)

Ansari, R.; Rouhi, S.; Ajori, S.

2016-06-01

Molecular dynamics (MD) simulations is used to study the adsorption of polyethylene (PE) and poly(ethylene oxide) (PEO) on the functionalized single-walled carbon nanotubes (SWCNTs). The effects of functionalization factor weight percent on the interaction energies of polymer chains with nanotubes are studied. Besides, the influences of different functionalization factors on the SWCNT/polymer interactions are investigated. It is shown that for both types of polymer chains, the largest interaction energies associates with the random O functionalized nanotubes. Besides, increasing temperature results in increasing the nanotube/polymer interaction energy. Considering the final shapes of adsorbed polymer chains on the SWCNTs, it is observed that the adsorbed conformations of PE chains are more contracted than those of PEO chains.

Modification of Side Chains of Conjugated Molecules and Polymers for Charge Mobility Enhancement and Sensing Functionality.

PubMed

Liu, Zitong; Zhang, Guanxin; Zhang, Deqing

2018-06-19

Organic semiconductors have received increasing attentions in recent years because of their promising applications in various optoelectronic devices. The key performance metric for organic semiconductors is charge carrier mobility, which is governed by the electronic structures of conjugated backbones and intermolecular/interchain π-π interactions and packing in both microscopic and macroscopic levels. For this reason, more efforts have been paid to the design and synthesis of conjugated frameworks for organic semiconductors with high charge mobilities. However, recent studies manifest that appropriate modifications of side chains that are linked to conjugated frameworks can improve the intermolecular/interchain packing order and boost charge mobilities. In this Account, we discuss our research results in context of modification of side chains in organic semiconductors for charge mobility enhancement. These include the following: (i) The lengths of alkyl chains in sulfur-rich thiepin-fused heteroacences can dramatically influence the intermolecular arrangements and orbital overlaps, ushering in different hole mobilities. Inversely, the lamellar stacking modes of alkyl chains in naphthalene diimide (NDI) derivatives with tetrathiafulvalene (TTF) units are affected by the structures of conjugated cores. (ii) The steric hindrances owing to the bulky branching chains can be weakened by partial replacement of the branching alkyl chains with linear ones for diketopyrrolopyrrole (DPP)-based D (donor)-A (acceptor) conjugated polymers. Such modification of side chains makes the polymer backbones more planar and thus interchain packing order and charge mobilities are improved. The incorporation of hydrophilic tri(ethylene glycol) (TEG) chains into the polymers also leads to improved interchain packing order. In particular, the polymer in which TEG side chains are distributed uniformly exhibits relatively high charge mobility without thermal annealing. (iii) The incorporation of urea groups in the side chains induces the polymer chains to pack more orderly and form large domains because of the additional H-bonding among urea groups. Accordingly, thin film mobilities of the conjugated D-A polymers with side chains entailing urea groups are largely boosted in comparison with those of polymers of the same backbones with either branching alkyl chains or branching/linear alkyl chains. (iv) The torsions of branching alkyl chains in conjugated D-A polymers can be inhibited to some extent upon incorporation of tiny amount of NMe 4 I in the thin film. As a result, the polymer thin films with NMe 4 I exhibit improved crystallinity, and charge mobilities can be boosted by more than 20 times. (v) Side chains with functional groups in the conjugated polymers can endow the thin film field-effect transistors (FETs) with sensing functionality. FETs with the conjugated polymer with -COOH groups in the side chains show sensitive, selective, and fast responses toward ammonia and amines, while FETs with the ultrathin films of the polymer containing tetra(ethylene glycol) (TEEG) in the side chains can sense alcohol vapors (in particular ethanol vapor) sensitively and selectively with fast response.

Solution‐crystallization and related phenomena in 9,9‐dialkyl‐fluorene polymers. II. Influence of side‐chain structure

PubMed Central

Perevedentsev, Aleksandr; Stavrinou, Paul N.; Smith, Paul

2015-01-01

ABSTRACT Solution‐crystallization is studied for two polyfluorene polymers possessing different side‐chain structures. Thermal analysis and temperature‐dependent optical spectroscopy are used to clarify the nature of the crystallization process, while X‐ray diffraction and scanning electron microscopy reveal important differences in the resulting microstructures. It is shown that the planar‐zigzag chain conformation termed the β‐phase, which is observed for certain linear‐side‐chain polyfluorenes, is necessary for the formation of so‐called polymer‐solvent compounds for these polymers. Introduction of alternating fluorene repeat units with branched side‐chains prevents formation of the β‐phase conformation and results in non‐solvated, i.e. melt‐crystallization‐type, polymer crystals. Unlike non‐solvated polymer crystals, for which the chain conformation is stabilized by its incorporation into a crystalline lattice, the β‐phase conformation is stabilized by complexation with solvent molecules and, therefore, its formation does not require specific inter‐chain interactions. The presented results clarify the fundamental differences between the β‐phase and other conformational/crystalline forms of polyfluorenes. © 2015 The Authors. Journal of Polymer Science Part B: Polymer Physics published by Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015, 53, 1492–1506 PMID:27546983

Electrohydrodynamics in nanochannels coated by mixed polymer brushes: effects of electric field strength and solvent quality

NASA Astrophysics Data System (ADS)

Cao, Qianqian; Tian, Xiu; You, Hao

2018-04-01

We examine the electrohydrodynamics in mixed polymer brush-coated nanochannels and the conformational dynamics of grafted polymers using molecular dynamics simulations. Charged (A) and neutral polymers (B) are alternately grafted on the channel surfaces. The effects of the electric field strength and solvent quality are addressed in detail. The dependence of electroosmotic flow characteristics and polymer conformational behavior on the solvent quality is influenced due to the change of the electric field strength. The enhanced electric field induces a collapse of the neutral polymer chains which adopt a highly extended conformation along the flow direction. However, the thickness of the charged polymer layer is affected weakly by the electric field, and even a slight swelling is identified for the A-B attraction case, implying the conformational coupling between two polymer species. Furthermore, the charged polymer chains incline entirely towards the electric field direction oppositely to the flow direction. More importantly, unlike the neutral polymer chains, the shape factor of the charged polymer chains, which is used to describe the overall shape of polymer chains, is reduced significantly with increasing the electric field strength, corresponding to a more coiled structure.

Structure-induced switching of interpolymer adhesion at a solid-polymer melt interface.

PubMed

Jiang, Naisheng; Sen, Mani; Zeng, Wenduo; Chen, Zhizhao; Cheung, Justin M; Morimitsu, Yuma; Endoh, Maya K; Koga, Tadanori; Fukuto, Masafumi; Yuan, Guangcui; Satija, Sushil K; Carrillo, Jan-Michael Y; Sumpter, Bobby G

2018-02-14

Here we report a link between the interfacial structure and adhesive property of homopolymer chains physically adsorbed (i.e., via physisorption) onto solids. Polyethylene oxide (PEO) was used as a model and two different chain conformations of the adsorbed polymer were created on silicon substrates via the well-established Guiselin's approach: "flattened chains" which lie flat on the solid and are densely packed, and "loosely adsorbed polymer chains" which form bridges jointing up nearby empty sites on the solid surface and cover the flattened chains. We investigated the adhesion properties of the two different adsorbed chains using a custom-built adhesion testing device. Bilayers of a thick PEO overlayer on top of the flattened chains or loosely adsorbed chains were subjected to the adhesion test. The results revealed that the flattened chains do not show any adhesion even with the chemically identical free polymer on top, while the loosely adsorbed chains exhibit adhesion. Neutron reflectivity experiments corroborated that the difference in the interfacial adhesion is not attributed to the interfacial brodening at the free polymer-adsorbed polymer interface. Instead, coarse-grained molecular dynamics simulation results suggest that the tail parts of the loosely adsorbed chains act as "connector molecules", bridging the free chains and substrate surface and improving the interfacial adhesion. These findings not only shed light on the structure-property relationship at the interface, but also provide a novel approach for developing sticking/anti-sticking technologies through precise control of the interfacial polymer nanostructures.

Polymer chain alignment and transistor properties of nanochannel-templated poly(3-hexylthiophene) nanowires

NASA Astrophysics Data System (ADS)

Oh, Seungjun; Hayakawa, Ryoma; Pan, Chengjun; Sugiyasu, Kazunori; Wakayama, Yutaka

2016-08-01

Nanowires of semiconducting poly(3-hexylthiophene) (P3HT) were produced by a nanochannel-template technique. Polymer chain alignment in P3HT nanowires was investigated as a function of nanochannel widths (W) and polymer chain lengths (L). We found that the ratio between chain length and channel width (L/W) was a key parameter as regards promoting polymer chain alignment. Clear dichroism was observed in polarized ultraviolet-visible (UV-Vis) absorption spectra only at a ratio of approximately L/W = 2, indicating that the L/W ratio must be optimized to achieve uniaxial chain alignment in the nanochannel direction. We speculate that an appropriate L/W ratio is effective in confining the geometries and conformations of polymer chains. This discussion was supported by theoretical simulations based on molecular dynamics. That is, the geometry of the polymer chains, including the distance and tilting angles of the chains in relation to the nanochannel surface, was dominant in determining the longitudinal alignment along the nanochannels. Thus prepared highly aligned polymer nanowire is advantageous for electrical carrier transport and has great potential for improving the device performance of field-effect transistors. In fact, a one-order improvement in carrier mobility was observed in a P3HT nanowire transistor.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Martinez, Andre P.; Carrillo, Jan-Michael Y.; Dobrynin, Andrey V.

The molecular weight and polydispersity of the chains in a polymer brush are critical parameters determining the brush properties. However, the characterization of polymer brushes is hindered by the vanishingly small mass of polymer present in brush layers. In this study, in order to obtain sufficient quantities of polymer for analysis, polymer brushes were grown from high surface area fibrous nylon membranes by ATRP. We synthesized the brushes with varying surface initiator densities, polymerization times, and amounts of sacrificial initiator, then cleaved from the substrate, and analyzed by GPC and NMR. Characterization showed that the surface-grown polymer chains were moremore » polydisperse and had lower average molecular weight compared to solution-grown polymers synthesized concurrently. Furthermore, the molecular weight distribution of the polymer brushes was observed to be bimodal, with a low molecular weight population of chains representing a significant mass fraction of the polymer chains at high surface initiator densities. Moreover, the origin of this low MW polymer fraction is proposed to be the termination of growing chains by recombination during the early stages of polymerization, a mechanism confirmed by molecular dynamics simulations of brush polymerization.« less

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.

The role of nanoparticle rigidity on the diffusion of linear polystyrene in a polymer nanocomposite

DOE PAGES

Miller, Brad; Imel, Adam E.; Holley, Wade; ...

2015-11-12

The impact of the inclusion of a nanoparticle in a polymer matrix on the dynamics of the polymer chains is an area of recent interest. In this article, we describe the role of nanoparticle rigidity or softness on the impact of the presence of that nanoparticle on the diffusive behavior of linear polymer chains. The neutron reflectivity results clearly show that the inclusion of 10 nm soft nanoparticles in a polymer matrix (R g ~ 20 nm) increases the diffusion coefficient of the linear polymer chain. Surprisingly, thermal analysis shows that these nanocomposites exhibit an increase in their glass transitionmore » temperature, which is incommensurate with an increase in free volume. Therefore, it appears that this effect is more complex than a simple plasticizing effect. Results from small-angle neutron scattering of the nanoparticles in solution show a structure that consists of a gel like core with a corona of free chain ends and loops. Furthermore, the increase in linear polymer diffusion may be related to an increase in constraint release mechanisms in the reptation of the polymer chain, in a similar manner to that which has been reported for the diffusion of linear polymer chains in the presence of star polymers.« less

The role of nanoparticle rigidity on the diffusion of linear polystyrene in a polymer nanocomposite

DOE Office of Scientific and Technical Information (OSTI.GOV)

Miller, Brad; Imel, Adam E.; Holley, Wade

The impact of the inclusion of a nanoparticle in a polymer matrix on the dynamics of the polymer chains is an area of recent interest. In this article, we describe the role of nanoparticle rigidity or softness on the impact of the presence of that nanoparticle on the diffusive behavior of linear polymer chains. The neutron reflectivity results clearly show that the inclusion of 10 nm soft nanoparticles in a polymer matrix (R g ~ 20 nm) increases the diffusion coefficient of the linear polymer chain. Surprisingly, thermal analysis shows that these nanocomposites exhibit an increase in their glass transitionmore » temperature, which is incommensurate with an increase in free volume. Therefore, it appears that this effect is more complex than a simple plasticizing effect. Results from small-angle neutron scattering of the nanoparticles in solution show a structure that consists of a gel like core with a corona of free chain ends and loops. Furthermore, the increase in linear polymer diffusion may be related to an increase in constraint release mechanisms in the reptation of the polymer chain, in a similar manner to that which has been reported for the diffusion of linear polymer chains in the presence of star polymers.« less

General approach to polymer chains confined by interacting boundaries

NASA Astrophysics Data System (ADS)

Freed, Karl F.; Dudowicz, Jacek; Stukalin, Evgeny B.; Douglas, Jack F.

2010-09-01

Polymer chains, confined to cavities or polymer layers with dimensions less than the chain radius of gyration, appear in many phenomena, such as gel chromatography, rubber elasticity, viscolelasticity of high molar mass polymer melts, the translocation of polymers through nanopores and nanotubes, polymer adsorption, etc. Thus, the description of how the constraints alter polymer thermodynamic properties is a recurrent theoretical problem. A realistic treatment requires the incorporation of impenetrable interacting (attractive or repulsive) boundaries, a process that introduces significant mathematical complications. The standard approach involves developing the generalized diffusion equation description of the interaction of flexible polymers with impenetrable confining surfaces into a discrete eigenfunction expansion, where the solutions are normally truncated at the first mode (the "ground state dominance" approximation). This approximation is mathematically well justified under conditions of strong confinement, i.e., a confinement length scale much smaller than the chain radius of gyration, but becomes unreliable when the polymers are confined to dimensions comparable to their typically nanoscale size. We extend a general approach to describe polymers under conditions of weak to moderate confinement and apply this semianalytic method specifically to determine the thermodynamics and static structure factor for a flexible polymer confined between impenetrable interacting parallel plate boundaries. The method is first illustrated by analyzing chain partitioning between a pore and a large external reservoir, a model system with application to chromatography. Improved agreement is found for the partition coefficients of a polymer chain in the pore geometry. An expression is derived for the structure factor S(k ) in a slit geometry to assist in more accurately estimating chain dimensions from scattering measurements for thin polymer films.

Structure of Cellulose Microfibrils in Primary Cell Walls from Collenchyma1[C][W][OA

PubMed Central

Thomas, Lynne H.; Forsyth, V. Trevor; Šturcová, Adriana; Kennedy, Craig J.; May, Roland P.; Altaner, Clemens M.; Apperley, David C.; Wess, Timothy J.; Jarvis, Michael C.

2013-01-01

In the primary walls of growing plant cells, the glucose polymer cellulose is assembled into long microfibrils a few nanometers in diameter. The rigidity and orientation of these microfibrils control cell expansion; therefore, cellulose synthesis is a key factor in the growth and morphogenesis of plants. Celery (Apium graveolens) collenchyma is a useful model system for the study of primary wall microfibril structure because its microfibrils are oriented with unusual uniformity, facilitating spectroscopic and diffraction experiments. Using a combination of x-ray and neutron scattering methods with vibrational and nuclear magnetic resonance spectroscopy, we show that celery collenchyma microfibrils were 2.9 to 3.0 nm in mean diameter, with a most probable structure containing 24 chains in cross section, arranged in eight hydrogen-bonded sheets of three chains, with extensive disorder in lateral packing, conformation, and hydrogen bonding. A similar 18-chain structure, and 24-chain structures of different shape, fitted the data less well. Conformational disorder was largely restricted to the surface chains, but disorder in chain packing was not. That is, in position and orientation, the surface chains conformed to the disordered lattice constituting the core of each microfibril. There was evidence that adjacent microfibrils were noncovalently aggregated together over part of their length, suggesting that the need to disrupt these aggregates might be a constraining factor in growth and in the hydrolysis of cellulose for biofuel production. PMID:23175754

Structure of cellulose microfibrils in primary cell walls from collenchyma.

PubMed

Thomas, Lynne H; Forsyth, V Trevor; Sturcová, Adriana; Kennedy, Craig J; May, Roland P; Altaner, Clemens M; Apperley, David C; Wess, Timothy J; Jarvis, Michael C

2013-01-01

In the primary walls of growing plant cells, the glucose polymer cellulose is assembled into long microfibrils a few nanometers in diameter. The rigidity and orientation of these microfibrils control cell expansion; therefore, cellulose synthesis is a key factor in the growth and morphogenesis of plants. Celery (Apium graveolens) collenchyma is a useful model system for the study of primary wall microfibril structure because its microfibrils are oriented with unusual uniformity, facilitating spectroscopic and diffraction experiments. Using a combination of x-ray and neutron scattering methods with vibrational and nuclear magnetic resonance spectroscopy, we show that celery collenchyma microfibrils were 2.9 to 3.0 nm in mean diameter, with a most probable structure containing 24 chains in cross section, arranged in eight hydrogen-bonded sheets of three chains, with extensive disorder in lateral packing, conformation, and hydrogen bonding. A similar 18-chain structure, and 24-chain structures of different shape, fitted the data less well. Conformational disorder was largely restricted to the surface chains, but disorder in chain packing was not. That is, in position and orientation, the surface chains conformed to the disordered lattice constituting the core of each microfibril. There was evidence that adjacent microfibrils were noncovalently aggregated together over part of their length, suggesting that the need to disrupt these aggregates might be a constraining factor in growth and in the hydrolysis of cellulose for biofuel production.

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kim, Bong-Gi; Jeong, Eun Jeong; Chung, Jong Won

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 themore » 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.« less

Structure of Irreversibly Adsorbed Star Polymers

NASA Astrophysics Data System (ADS)

Akgun, Bulent; Aykan, Meryem Seyma; Canavar, Seda; Satija, Sushil K.; Uhrig, David; Hong, Kunlun

Formation of irreversibly adsorbed polymer chains on solid substrates have a huge impact on the wetting, glass transition, aging and polymer chain mobility in thin films. In recent years there has been many reports on the formation, kinetics and dynamics of these layers formed by linear homopolymers. Recent studies showed that by varying the number of polymer arms and arm molecular weight one can tune the glass transition temperature of thin polymer films. Using polymer architecture as a tool, the behavior of thin films can be tuned between the behavior of linear chains and soft colloids. We have studied the effect of polymer chain architecture on the structure of dead layer using X-ray reflectivity (XR) and atomic force microscopy. Layer thicknesses and densities of flattened and loosely adsorbed chains has been measured for linear, 4-arm, and 8-arm star polymers with identical total molecular weight as a function of substrate surface energy, annealing temperature and annealing time. Star polymers have been synthesized using anionic polymerization. XR measurements showed that 8-arm star PS molecules form the densest and the thickest dead layers among these three molecules.

Powder metallurgy inspired low-temperature fabrication of high-performance stereocomplexed polylactide products with good optical transparency

PubMed Central

Bai, Dongyu; Liu, Huili; Bai, Hongwei; Zhang, Qin; Fu, Qiang

2016-01-01

Stereocomplexation between enantiomeric poly(l-lactide) (PLLA) and poly(d-lactide) (PDLA) provides an avenue to greatly enhance performance of eco-friendly polylactide (PLA). Unfortunately, although the manufacturing of semicrystalline polymers generally involves melt processing, it is still hugely challenging to create high-performance stereocomplexed polylactide (sc-PLA) products from melt-processed high-molecular-weight PLLA/PDLA blends due to the weak crystallization memory effect of stereocomplex (sc) crystallites after complete melting as well as the substantial degradation of PLA chains at elevated melt-processing temperatures of ca. 240–260 °C. Inspired by the concept of powder metallurgy, here we report a new facile route to address these obstacles by sintering of sc-PLA powder at temperatures as low as 180–210 °C, which is distinctly different from traditional sintering of polymer powders performed at temperatures far exceeding their melting temperatures. The enantiomeric PLA chain segments from adjacent powder particles can interdiffuse across particle interfaces and co-crystallize into new sc crystallites capable of tightly welding the interfaces during the low-temperature sintering process, and thus highly transparent sc-PLA products with outstanding heat resistance, mechanical strength, and hydrolytic stability have been successfully fabricated for the first time. PMID:26837848

Powder metallurgy inspired low-temperature fabrication of high-performance stereocomplexed polylactide products with good optical transparency

NASA Astrophysics Data System (ADS)

Bai, Dongyu; Liu, Huili; Bai, Hongwei; Zhang, Qin; Fu, Qiang

2016-02-01

Stereocomplexation between enantiomeric poly(L-lactide) (PLLA) and poly(D-lactide) (PDLA) provides an avenue to greatly enhance performance of eco-friendly polylactide (PLA). Unfortunately, although the manufacturing of semicrystalline polymers generally involves melt processing, it is still hugely challenging to create high-performance stereocomplexed polylactide (sc-PLA) products from melt-processed high-molecular-weight PLLA/PDLA blends due to the weak crystallization memory effect of stereocomplex (sc) crystallites after complete melting as well as the substantial degradation of PLA chains at elevated melt-processing temperatures of ca. 240-260 °C. Inspired by the concept of powder metallurgy, here we report a new facile route to address these obstacles by sintering of sc-PLA powder at temperatures as low as 180-210 °C, which is distinctly different from traditional sintering of polymer powders performed at temperatures far exceeding their melting temperatures. The enantiomeric PLA chain segments from adjacent powder particles can interdiffuse across particle interfaces and co-crystallize into new sc crystallites capable of tightly welding the interfaces during the low-temperature sintering process, and thus highly transparent sc-PLA products with outstanding heat resistance, mechanical strength, and hydrolytic stability have been successfully fabricated for the first time.

Powder metallurgy inspired low-temperature fabrication of high-performance stereocomplexed polylactide products with good optical transparency.

PubMed

Bai, Dongyu; Liu, Huili; Bai, Hongwei; Zhang, Qin; Fu, Qiang

2016-02-03

Stereocomplexation between enantiomeric poly(l-lactide) (PLLA) and poly(d-lactide) (PDLA) provides an avenue to greatly enhance performance of eco-friendly polylactide (PLA). Unfortunately, although the manufacturing of semicrystalline polymers generally involves melt processing, it is still hugely challenging to create high-performance stereocomplexed polylactide (sc-PLA) products from melt-processed high-molecular-weight PLLA/PDLA blends due to the weak crystallization memory effect of stereocomplex (sc) crystallites after complete melting as well as the substantial degradation of PLA chains at elevated melt-processing temperatures of ca. 240-260 °C. Inspired by the concept of powder metallurgy, here we report a new facile route to address these obstacles by sintering of sc-PLA powder at temperatures as low as 180-210 °C, which is distinctly different from traditional sintering of polymer powders performed at temperatures far exceeding their melting temperatures. The enantiomeric PLA chain segments from adjacent powder particles can interdiffuse across particle interfaces and co-crystallize into new sc crystallites capable of tightly welding the interfaces during the low-temperature sintering process, and thus highly transparent sc-PLA products with outstanding heat resistance, mechanical strength, and hydrolytic stability have been successfully fabricated for the first time.

Asymmetric Alkyl Side-Chain Engineering of Naphthalene Diimide-Based n-Type Polymers for Efficient All-Polymer Solar Cells.

PubMed

Jia, Tao; Li, Zhenye; Ying, Lei; Jia, Jianchao; Fan, Baobing; Zhong, Wenkai; Pan, Feilong; He, Penghui; Chen, Junwu; Huang, Fei; Cao, Yong

2018-02-13

The design and synthesis of three n-type conjugated polymers based on a naphthalene diimide-thiophene skeleton are presented. The control polymer, PNDI-2HD, has two identical 2-hexyldecyl side chains, and the other polymers have different alkyl side chains; PNDI-EHDT has a 2-ethylhexyl and a 2-decyltetradecyl side chain, and PNDI-BOOD has a 2-butyloctyl and a 2-octyldodecyl side chain. These copolymers with different alkyl side chains exhibit higher melting and crystallization temperatures, and stronger aggregation in solution, than the control copolymer PNDI-2HD that has the same side chain. Polymer solar cells based on the electron-donating copolymer PTB7-Th and these novel copolymers exhibit nearly the same open-circuit voltage of 0.77 V. Devices based on the copolymer PNDI-BOOD with different side chains have a power-conversion efficiency of up to 6.89%, which is much higher than the 4.30% obtained with the symmetric PNDI-2HD. This improvement can be attributed to the improved charge-carrier mobility and the formation of favorable film morphology. These observations suggest that the molecular design strategy of incorporating different side chains can provide a new and promising approach to developing n-type conjugated polymers. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Structural variability in Cu(I) and Ag(I) coordination polymers with a flexible dithione ligand: Synthesis, crystal structure, microbiological and theoretical studies

DOE Office of Scientific and Technical Information (OSTI.GOV)

Beheshti, Azizolla, E-mail: a.beheshti@scu.ac.ir; Nozarian, Kimia; Babadi, Susan Soleymani

Two new compounds namely [Cu(SCN)(µ-L)]{sub n} (1) and ([Ag (µ{sub 2}-L)](ClO{sub 4})){sub n} (2) have been synthesized at room temperature by one-pot reactions between the 1,1-(1,4-butanediyl)bis(1,3-dihydro-3-methyl-1H-imidazole- 2-thione) (L) and appropriate copper(I) and silver(I) salts. These polymers have been characterized by single crystal X-ray diffraction, XRPD, TGA, elemental analysis, infrared spectroscopy, antibacterial activity and scanning probe microscopy studies. In the crystal structure of 1, copper atoms have a distorted trigonal planar geometry with a CuS{sub 2}N coordination environment. Each of the ligands in the structure of 1 acting as a bidentate S-bridging ligand to form a 1D chain structure. Additionally, themore » adjacent 1D chains are interconnected by the intermolecular C-H…S interactions to create a 2D network structure. In contrast to 1, in the cationic 3D structure of 2 each of the silver atoms exhibits an AgS{sub 4} tetrahedral geometry with 4-membered Ag{sub 2}S{sub 2} rings. In the structure of 2, the flexible ligand adopts two different conformations; gauche-anti-gauche and anti-anti-anti. The antibacterial studies of these polymers showed that polymer 2 is more potent antibacterial agent than 1. Scanning probe microscopy (SPM) study of the treated bacteria was carried out to investigate the structural changes cause by the interactions between the polymers and target bacteria. Theoretical study of polymer 1 investigated by the DFT calculations indicates that observed transitions at 266 nm and 302 nm in the UV–vis spectrum could be attributed to the π→π* and MLCT transitions, respectively. - Graphical abstract: Two new Cu(I) and Ag(I) coordination polymers have been have been synthesized by one-pot reactions. Copper complex has a 2D non-covalent structure, but silver compound is a 3D coordination compound. These compounds have effective antibacterial activity. - Highlights: • Cu(I) and Ag(I) based coordination polymers have different network structures. • Ag(I) polymer has more antibacterial activity than Cu(I) polymer. • DFT calculations of Cu(I) polymer has been investigated. • Cu(I) and Ag(I) polymers can destroy the structure of chromosomal and plasmid DNA.« less

Scale-Dependent Stiffness and Internal Tension of a Model Brush Polymer

NASA Astrophysics Data System (ADS)

Berezney, John P.; Marciel, Amanda B.; Schroeder, Charles M.; Saleh, Omar A.

2017-09-01

Bottle-brush polymers exhibit closely grafted side chains that interact by steric repulsion, thereby causing stiffening of the main polymer chain. We use single-molecule elasticity measurements of model brush polymers to quantify this effect. We find that stiffening is only significant on long length scales, with the main chain retaining flexibility on short scales. From the elasticity data, we extract an estimate of the internal tension generated by side-chain repulsion; this estimate is consistent with the predictions of blob-based scaling theories.

Effect of short-chain branching on interfacial polymer structure and dynamics under shear flow.

PubMed

Jeong, Sohdam; Kim, Jun Mo; Cho, Soowon; Baig, Chunggi

2017-11-22

We present a detailed analysis on the effect of short-chain branches on the structure and dynamics of interfacial chains using atomistic nonequilibrium molecular dynamics simulations of confined polyethylene melts in a wide range of shear rates. The intrinsically fast random motions of the short branches constantly disturb the overall chain conformation, leading to a more compact and less deformed chain structure of the short-chain branched (SCB) polymer against the imposed flow field in comparison with the corresponding linear polymer. Moreover, such highly mobile short branches along the backbone of the SCB polymer lead to relatively weaker out-of-plane wagging dynamics of interfacial chains, with highly curvy backbone structures in the intermediate flow regime. In conjunction with the contribution of short branches (as opposed to that of the backbone) to the total interfacial friction between the chains and the wall, the SCB polymer shows a nearly constant behavior in the degree of slip (d s ) with respect to shear rate in the weak-to-intermediate flow regimes. On the contrary, in the strong flow regime where irregular chain rotation and tumbling dynamics occur via intensive dynamical collisions between interfacial chains and the wall, an enhancement effect on the chain detachment from the wall, caused by short branches, leads to a steeper increase in d s for the SCB polymer than for the linear polymer. Remarkably, the SCB chains at the interface exhibit two distinct types of rolling mechanisms along the backbone, with a half-dumbbell mesoscopic structure at strong flow fields, in addition to the typical hairpin-like tumbling behavior displayed by the linear chains.

Understanding the interfacial chain dynamics of fiber-reinforced polymer composite

NASA Astrophysics Data System (ADS)

Goswami, Monojoy; Carrillo, Jan-Michael; Naskar, Amit; Sumpter, Bobby

The polymer-fiber interface plays a major role in determining the structural and dynamical properties of fiber reinforced composite materials. We utilized LAMMPS MD package to understand the interfacial properties at the nanoscale. Coarse-grained flexible polymer chains are introduced to compare the various structures and dynamics of the polymer chains. Our preliminary simulation study shows that the rigidity of the polymer chain affects the interfacial morphology and dynamics of the chain on a flat surface. In this work, we identified the `immobile inter-phase' morphology and relate it to rheological properties. We calculated the viscoelastic properties, e.g., shear modulus and storage modulus, which are compared with experiments. MD simulations are used to show the variation of viscoelastic properties with polymer volume fraction. The nanoscale segmental and chain relaxation are calculated from the MD simulations and compared to the experimental data. These observations will be able to identify the fundamental physics behind the effect of the polymer-fiber interactions and orientation of the fiber to the overall rheological properties of the fiber reinforced polymer matrix. Funding for the project was provided by ORNLs Laboratory Directed Research and Development (LDRD) program.

Molecular weight dependent structure and charge transport in MAPLE-deposited poly(3-hexylthiophene) thin films

DOE PAGES

Dong, Ban Xuan; Smith, Mitchell; Strzalka, Joseph; ...

2018-02-06

In this work, poly(3-hexylthiophene) (P3HT) films prepared using the matrix-assisted pulsed laser evaporation (MAPLE) technique are shown to possess morphological structures that are dependent on molecular weight (MW). Specifically, the structures of low MW samples of MAPLE-deposited film are composed of crystallites/aggregates embedded within highly disordered environments, whereas those of high MW samples are composed of aggregated domains connected by long polymer chains. Additionally, the crystallite size along the side-chain (100) direction decreases, whereas the conjugation length increases with increasing molecular weight. This is qualitatively similar to the structure of spin-cast films, though the MAPLE-deposited films are more disordered. In-planemore » carrier mobilities in the MAPLE-deposited samples increase with MW, consistent with the notion that longer chains bridge adjacent aggregated domains thereby facilitating more effective charge transport. The carrier mobilities in the MAPLE-deposited simples are consistently lower than those in the solvent-cast samples for all molecular weights, consistent with the shorter conjugation length in samples prepared by this deposition technique.« less

Molecular weight dependent structure and charge transport in MAPLE-deposited poly(3-hexylthiophene) thin films

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dong, Ban Xuan; Smith, Mitchell; Strzalka, Joseph

In this work, poly(3-hexylthiophene) (P3HT) films prepared using the matrix-assisted pulsed laser evaporation (MAPLE) technique are shown to possess morphological structures that are dependent on molecular weight (MW). Specifically, the structures of low MW samples of MAPLE-deposited film are composed of crystallites/aggregates embedded within highly disordered environments, whereas those of high MW samples are composed of aggregated domains connected by long polymer chains. Additionally, the crystallite size along the side-chain (100) direction decreases, whereas the conjugation length increases with increasing molecular weight. This is qualitatively similar to the structure of spin-cast films, though the MAPLE-deposited films are more disordered. In-planemore » carrier mobilities in the MAPLE-deposited samples increase with MW, consistent with the notion that longer chains bridge adjacent aggregated domains thereby facilitating more effective charge transport. The carrier mobilities in the MAPLE-deposited simples are consistently lower than those in the solvent-cast samples for all molecular weights, consistent with the shorter conjugation length in samples prepared by this deposition technique.« less

Polymer in a pore: Effect of confinement on the free energy barrier

NASA Astrophysics Data System (ADS)

Kumar, Sanjiv; Kumar, Sanjay

2018-06-01

We investigate the transfer of a polymer chain from cis- side to trans- side through two types of pores: cone-shaped channel and flat-channel. Using the exact enumeration technique, we obtain the free energy landscapes of a polymer chain for such systems. We have also calculated the free-energy barrier of a polymer chain attached to the edge of the pore. The model system allows us to calculate the force required to pull polymer from the pore and stall-force to confine polymer within the pore.

Chain Conformation near the Buried Interface in Nanoparticle-Stabilized Polymer Thin Films

DOE Office of Scientific and Technical Information (OSTI.GOV)

Barkley, Deborah A.; Jiang, Naisheng; Sen, Mani

It is known that when nanoparticles are added to polymer thin films, they often migrate to the film-substrate interface and form an “immobile interfacial layer”, which has been believed as the origin of suppression of dewetting. We here report an alternative mechanism of dewetting suppression from the structural aspect of a polymer. Dodecane thiol-functionalized gold (Au) nanoparticles embedded in PS thin films prepared on Si substrates were used as a model. It was found that thermal annealing promotes irreversible polymer adsorption onto the substrate surface along with the surface migration of the nanoparticles. We also revealed that the surface migrationmore » causes additional nanoconfined space for the adsorbed polymer chains. As a result, the self-organization process of the strongly adsorbed polymer chains on the solid surface was so hindered that the chain conformations were randomized and expanded in the film normal direction. Here, the resultant chain conformation allows the interpenetration between free chains and the adsorbed chains, promoting adhesion and hence stabilizing the thin film.« less

Chain Conformation near the Buried Interface in Nanoparticle-Stabilized Polymer Thin Films

DOE PAGES

Barkley, Deborah A.; Jiang, Naisheng; Sen, Mani; ...

2017-09-26

It is known that when nanoparticles are added to polymer thin films, they often migrate to the film-substrate interface and form an “immobile interfacial layer”, which has been believed as the origin of suppression of dewetting. We here report an alternative mechanism of dewetting suppression from the structural aspect of a polymer. Dodecane thiol-functionalized gold (Au) nanoparticles embedded in PS thin films prepared on Si substrates were used as a model. It was found that thermal annealing promotes irreversible polymer adsorption onto the substrate surface along with the surface migration of the nanoparticles. We also revealed that the surface migrationmore » causes additional nanoconfined space for the adsorbed polymer chains. As a result, the self-organization process of the strongly adsorbed polymer chains on the solid surface was so hindered that the chain conformations were randomized and expanded in the film normal direction. Here, the resultant chain conformation allows the interpenetration between free chains and the adsorbed chains, promoting adhesion and hence stabilizing the thin film.« less

Anomalous charge transport in conjugated polymers reveals underlying mechanisms of trapping and percolation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mollinger, Sonya A.; Salleo, Alberto; Spakowitz, Andrew J.

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 transportmore » on single polymer chains is characterized by the ability of the charge to navigate around kinks and loops in the chain. Lastly, 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.« less

Anomalous charge transport in conjugated polymers reveals underlying mechanisms of trapping and percolation

DOE PAGES

Mollinger, Sonya A.; Salleo, Alberto; Spakowitz, Andrew J.

2016-11-10

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 transportmore » on single polymer chains is characterized by the ability of the charge to navigate around kinks and loops in the chain. Lastly, 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.« less

Phase separation of a Lennard-Jones fluid interacting with a long, condensed polymer chain: implications for the nuclear body formation near chromosomes.

PubMed

Oh, Inrok; Choi, Saehyun; Jung, YounJoon; Kim, Jun Soo

2015-08-28

Phase separation in a biological cell nucleus occurs in a heterogeneous environment filled with a high density of chromatins and thus it is inevitably influenced by interactions with chromatins. As a model system of nuclear body formation in a cell nucleus filled with chromatins, we simulate the phase separation of a low-density Lennard-Jones (LJ) fluid interacting with a long, condensed polymer chain. The influence of the density variation of LJ particles above and below the phase boundary and the role of attractive interactions between LJ particles and polymer segments are investigated at a fixed value of strong self-interaction between LJ particles. For a density of LJ particles above the phase boundary, phase separation occurs and a dense domain of LJ particles forms irrespective of interactions with the condensed polymer chain whereas its localization relative to the polymer chain is determined by the LJ-polymer attraction strength. Especially, in the case of moderately weak attractions, the domain forms separately from the polymer chain and subsequently associates with the polymer chain. When the density is below the phase boundary, however, the formation of a dense domain is possible only when the LJ-polymer attraction is strong enough, for which the domain grows in direct contact with the interacting polymer chain. In this work, different growth behaviors of LJ particles result from the differences in the density of LJ particles and in the LJ-polymer interaction, and this work suggests that the distinct formation of activity-dependent and activity-independent nuclear bodies (NBs) in a cell nucleus may originate from the differences in the concentrations of body-specific NB components and in their interaction with chromatins.

Translocation time of a polymer chain through an energy gradient nanopore

NASA Astrophysics Data System (ADS)

Luo, Meng-Bo; Zhang, Shuang; Wu, Fan; Sun, Li-Zhen

2017-06-01

The translocation time of a polymer chain through an interaction energy gradient nanopore was studied by Monte Carlo simulations and the Fokker-Planck equation with double-absorbing boundary conditions. Both the simulation and calculation revealed three different behaviors for polymer translocation. These behaviors can be explained qualitatively from free-energy landscapes obtained for polymer translocation at different parameters. Results show that the translocation time of a polymer chain through a nanopore can be tuned by suitably designing the interaction energy gradient.

Influence of the nematic order on the rheology and conformation of stretched comb-like liquid crystalline polymers

NASA Astrophysics Data System (ADS)

Fourmaux-Demange, V.; Brûlet, A.; Boué, F.; Davidson, P.; Keller, P.; Cotton, J. P.

2000-04-01

We have studied the rheology and the conformation of stretched comb-like liquid-crystalline polymers. Both the influence of the comb-like structure and the specific effect of the nematic interaction on the dynamics are investigated. For this purpose, two isomers of a comb-like polymetacrylate polymer, of well-defined molecular weights, were synthesized: one displays a nematic phase over a wide range of temperature, the other one has only an isotropic phase. Even with high degrees of polymerization N, between 40 and 1000, the polymer chains studied were not entangled. The stress-strain curves during the stretching and relaxation processes show differences between the isotropic and nematic comb-like polymers. They suggest that, in the nematic phase, the chain dynamics is more cooperative than for a usual linear polymer. Small-angle neutron scattering has been used in order to determine the evolution of the chain conformation after stretching, as a function of the duration of relaxation t_r. The conformation can be described with two parameters only: λ_p, the global deformation of the polymer chain, and p, the number of statistical units of locally relaxed sub-chains. For the comb-like polymer, the chain deformation is pseudo-affine: λ_p is always smaller than λ (the deformation ratio of the whole sample). In the isotropic phase, λ_p has a constant value, while p increases as t_r. This latter behavior is not that expected for non-entangled chains, in which p varies as {t_r}^{1/2} (Rouse model). In the nematic phase, λ_p decreases as a stretched exponential function of t_r, while p remains constant. The dynamics of the comb-like polymers is discussed in terms of living clusters from which junctions are produced by interactions between side chains. The nematic interaction increases the lifetime of these junctions and, strikingly, the relaxation is the same at all scales of the whole polymer chain.

Stretching of Single Polymer Chains Using the Atomic Force Microscope

NASA Astrophysics Data System (ADS)

Ortiz, C.; van der Vegte, E. W.; van Swieten, E.; Robillard, G. T.; Hadziioannou, G.

1998-03-01

A variety of macroscopic phenomenon involve "nanoscale" polymer deformation including rubber elasticity, shear yielding, strain hardening, stress relaxation, fracture, and flow. With the advent of new and improved experimental techniques, such as the atomic force microscope (AFM), the probing of physical properties of polymers has reached finer and finer scales. The development of mixed self-assembling monolayer techniques and the chemical functionalization of AFM probe tips has allowed for mechanical experiments on single polymer chains of molecular dimensions. In our experiments, mixed monolayers are prepared in which end-functionalized, flexible polymer chains of thiol-terminated poly(methacrylic acid) are covalently bonded, isolated, and randomly distributed on gold substrates. The coils are then imaged, tethered to a gold-coated AFM tip, and stretched between the tip and the substrate in a conventional force / distance experiment. An increase in the attractive force due to entropic, elastic resistance to stretching, as well as fracture of the polymer chain is observed. The effect of chain stiffness, topological constraints, strain rate, mechanical hysteresis, and stress relaxation were investigated. Force modulation techniques were also employed in order to image the viscoelastic character of the polymer chains. Parallel work includes similar studies of biological systems such as wheat gluten proteins and polypeptides.

Syntheses, structures and luminescent properties of lanthanide coordination polymers assembled from imidazophenanthroline derivative and oxalate ligands

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhao, Hui; Sun, Xiao-Xia; Hu, Huai-Ming, E-mail: ChemHu1@NWU.EDU.CN

2017-01-15

Nine new lanthanide coordination polymers, namely, [Ln(Hsfpip)(ox){sub 0.5}(H{sub 2}O)]{sub n}·2n(H{sub 2}O) ((Ln=Eu (1), Tb (2), Dy (3), Ho (4), Er (5), Yb (6), Y(7)), [Ln(H{sub 2}sfpip)(ox)(H{sub 2}O){sub 4}]{sub n}·2n(H{sub 2}O) (Ln=Nd (8) Sm (9)), [H{sub 2}ox=oxalic acid, H{sub 3}sfpip=2-(2,4-disulfophenyl)imidazo(4,5-f)(1,10)-phenanthroline] have been synthesized under hydrothermal conditions and characterized by IR spectra, elemental analysis, powder X-ray diffraction and single crystal X-ray diffraction. When sodium oxalate is added, the reactions of lanthanide ions with H{sub 3}sfpip resulted in two types of structures. Compounds 1–7 are obtained at pH 5.0 and exhibit 3D tfz-d networks with ox{sup 2−} anions as linkers to bridge themore » adjacent layers. Compounds 8–9 are obtained at pH 2.0, and display a 1D chain which is further extended to a 3D supramolecular framework through intermolecular hydrogen bonds and π-π interactions. The structural variation from compounds 1–7 to 8–9 can attribute to the pH effect on construction of lanthanide coordination polymers. Moreover, the thermal stabilities and luminescence properties of 1–9 were also investigated. - Graphical abstract: Nine new lanthanide coordination polymers have been synthesized under hydrothermal conditions. Compounds 1–7 exhibit a 3D tfz-d network. Compounds 8–9 display a 1D chain structure. The structural variation from compounds 1–7 to 8–9 can attribute to the pH effect on construction of lanthanide coordination polymers. - Highlights: • Nine lanthanide coordination polymers were prepared under hydrothermal conditions. • Their crystal structures have been determined. • The luminescence and thermal stabilities were studied in the solid state.« less

Unexpected power-law stress relaxation of entangled ring polymers

PubMed Central

KAPNISTOS, M.; LANG, M.; PYCKHOUT-HINTZEN, W.; RICHTER, D.; CHO, D.; CHANG, T.

2016-01-01

After many years of intense research, most aspects of the motion of entangled polymers have been understood. Long linear and branched polymers have a characteristic entanglement plateau and their stress relaxes by chain reptation or branch retraction, respectively. In both mechanisms, the presence of chain ends is essential. But how do entangled polymers without ends relax their stress? Using properly purified high-molar-mass ring polymers, we demonstrate that these materials exhibit self-similar dynamics, yielding a power-law stress relaxation. However, trace amounts of linear chains at a concentration almost two decades below their overlap cause an enhanced mechanical response. An entanglement plateau is recovered at higher concentrations of linear chains. These results constitute an important step towards solving an outstanding problem of polymer science and are useful for manipulating properties of materials ranging from DNA to polycarbonate. They also provide possible directions for tuning the rheology of entangled polymers. PMID:18953345

Exploring Alkyl Chains in Benzobisthiazole-Naphthobisthiadiazole Polymers: Impact on Solar-Cell Performance, Crystalline Structures, and Optoelectronics.

PubMed

Al-Naamani, Eman; Gopal, Anesh; Ide, Marina; Osaka, Itaru; Saeki, Akinori

2017-11-01

The shapes and lengths of the alkyl chains of conjugated polymers greatly affect the efficiencies of organic photovoltaic devices. This often results in a trade-off between solubility and self-organizing behavior; however, each material has specific optimal chains. Here we report on the effect of alkyl side chains on the film morphologies, crystallinities, and optoelectronic properties of new benzobisthiazole-naphthobisthiadiazole (PBBT-NTz) polymers. The power conversion efficiencies (PCEs) of linear-branched and all-branched polymers range from 2.5% to 6.6%; the variations in these PCEs are investigated by atomic force microscopy, two-dimensional X-ray diffraction (2D-GIXRD), and transient photoconductivity techniques. The best-performing linear-branched polymer, bearing dodecyl and decyltetradecyl chains (C12-DT), exhibits nanometer-scale fibers along with the highest crystallinity, comprising predominant edge-on and partial face-on orientations. This morphology leads to the highest photoconductivity and the longest carrier lifetime. These results highlight the importance of long alkyl chains for inducing intermolecular stacking, which is in contrast to observations made for analogous previously reported polymers.

Stochastic entangled chain dynamics of dense polymer solutions.

PubMed

Kivotides, Demosthenes; Wilkin, S Louise; Theofanous, Theo G

2010-10-14

We propose an adjustable-parameter-free, entangled chain dynamics model of dense polymer solutions. The model includes the self-consistent dynamics of molecular chains and solvent by describing the former via coarse-grained polymer dynamics that incorporate hydrodynamic interaction effects, and the latter via the forced Stokes equation. Real chain elasticity is modeled via the inclusion of a Pincus regime in the polymer's force-extension curve. Excluded volume effects are taken into account via the combined action of coarse-grained intermolecular potentials and explicit geometric tracking of chain entanglements. We demonstrate that entanglements are responsible for a new (compared to phantom chain dynamics), slow relaxation mode whose characteristic time scale agrees very well with experiment. Similarly good agreement between theory and experiment is also obtained for the equilibrium chain size. We develop methods for the solution of the model in periodic flow domains and apply them to the computation of entangled polymer solutions in equilibrium. We show that the number of entanglements Π agrees well with the number of entanglements expected on the basis of tube theory, satisfactorily reproducing the latter's scaling of Π with the polymer volume fraction φ. Our model predicts diminishing chain size with concentration, thus vindicating Flory's suggestion of excluded volume effects screening in dense solutions. The predicted scaling of chain size with φ is consistent with the heuristic, Flory theory based value.

Note: A simple picture of subdiffusive polymer motion from stochastic simulations

NASA Astrophysics Data System (ADS)

Gniewek, Pawel; Kolinski, Andrzej

2011-02-01

Entangled polymer solutions and melts exhibit unusual frictional properties. In the entanglement limit self-diffusion coefficient of long flexible polymers decays with the second power of chain length and viscosity increases with 3-3.5 power of chain length.1 It is very difficult to provide detailed molecular-level explanation of the entanglement effect.2 Perhaps, the problem of many entangled polymer chains is the most complex multibody issue of classical physics. There are different approaches to polymer melt dynamics. Some of these recognize hydrodynamic interactions as a dominant term, while topological constraints for polymer chains are assumed as a secondary factor. Other theories consider the topological constraints as the most important factors controlling polymer dynamics. Herman and co-workers describe polymer dynamics in melts, as a lateral sliding of a chain along other chains until complete mutual disentanglement. Despite the success in explaining the power-laws for viscosity, the model has some limitations. First of all, memory effects are ignored, that is, polymer segments are treated independently. Also, each entanglement/obstacle is treated as a separate entity, which is certainly a simplification of the memory effect problem. In addition to that, correlated motions of segments are addressed within the framework of renormalized Rouse-chain theory,7 without calling any topological entanglements in advance. This approach leads to the generalized Langevin equation characterized by distinct memory kernels describing local and nonlocal segment correlations or to the Smoluchowski equation in which the segments' mobility is treated as a stochastic variable.11 Both models describe the polymer segments motion at a microscopic level. An interesting alternative is to solve the integrodifferential equation for the chain relaxation with a sophisticated kernel function.12 The design of the kernel function is based on a mesoscopic description of the polymer melt. These theories explain some experimental data, although the description of the crossover between the Rouse and non-Rouse behavior is not satisfactory. Obviously, within the scope of a short note we cannot review all theoretical concepts of the polymer melt dynamics. Here we focus just on the interpretation of the observed single segment autocorrelation function.

Chain conformations and phase behavior of conjugated polymers.

PubMed

Kuei, Brooke; Gomez, Enrique D

2016-12-21

Conjugated polymers may play an important role in various emerging optoelectronic applications because they combine the chemical versatility of organic molecules and the flexibility, stretchability and toughness of polymers with semiconducting properties. Nevertheless, in order to achieve the full potential of conjugated polymers, a clear description of how their structure, morphology, and macroscopic properties are interrelated is needed. We propose that the starting point for understanding conjugated polymers includes understanding chain conformations and phase behavior. Efforts to predict and measure the persistence length have significantly refined our intuition of the chain stiffness, and have led to predictions of nematic-to-isotropic transitions. Exploring mixing between conjugated polymers and small molecules or other polymers has demonstrated tremendous advancements in attaining the needed properties for various optoelectronic devices. Current efforts continue to refine our knowledge of chain conformations and phase behavior and the factors that influence these properties, thereby providing opportunities for the development of novel optoelectronic materials based on conjugated polymers.

Molecular Dynamics Modeling of PPTA Crystals in Aramid Fibers

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mercer, Brian Scott

2016-05-19

In this work, molecular dynamics modeling is used to study the mechanical properties of PPTA crystallites, which are the fundamental microstructural building blocks of polymer aramid bers such as Kevlar. Particular focus is given to constant strain rate axial loading simulations of PPTA crystallites, which is motivated by the rate-dependent mechanical properties observed in some experiments with aramid bers. In order to accommodate the covalent bond rupture that occurs in loading a crystallite to failure, the reactive bond order force eld ReaxFF is employed to conduct the simulations. Two major topics are addressed: The rst is the general behavior ofmore » PPTA crystallites under strain rate loading. Constant strain rate loading simulations of crystalline PPTA reveal that the crystal failure strain increases with increasing strain rate, while the modulus is not a ected by the strain rate. Increasing temperature lowers both the modulus and the failure strain. The simulations also identify the C N bond connecting the aromatic rings as weakest primary bond along the backbone of the PPTA chain. The e ect of chain-end defects on PPTA micromechanics is explored, and it is found that the presence of a chain-end defect transfers load to the adjacent chains in the hydrogen-bonded sheet in which the defect resides, but does not in uence the behavior of any other chains in the crystal. Chain-end defects are found to lower the strength of the crystal when clustered together, inducing bond failure via stress concentrations arising from the load transfer to bonds in adjacent chains near the defect site. The second topic addressed is the nature of primary and secondary bond failure in crystalline PPTA. Failure of both types of bonds is found to be stochastic in nature and driven by thermal uctuations of the bonds within the crystal. A model is proposed which uses reliability theory to model bonds under constant strain rate loading as components with time-dependent failure rate functions. The model is shown to work well for predicting the onset of primary backbone bond failure, as well as the onset of secondary bond failure via chain slippage for the case of isolated non-interacting chain-end defects.« less

The role of living/controlled radical polymerization in the formation of improved imprinted polymers.

PubMed

Salian, Vishal D; Vaughan, Asa D; Byrne, Mark E

2012-06-01

In this work, living/controlled radical polymerization (LRP) is compared with conventional free radical polymerization in the creation of highly and weakly cross-linked imprinted poly(methacrylic acid-co-ethylene glycol dimethacrylate) networks. It elucidates, for the first time, the effect of LRP on the chain level and begins to explain why the efficiency of the imprinting process is improved using LRP. Imprinted polymers produced via LRP exhibited significantly higher template affinity and capacity compared with polymers prepared using conventional methods. The use of LRP in the creation of highly cross-linked imprinted polymers resulted in a fourfold increase in binding capacity without a decrease in affinity; whereas weakly cross-linked gels demonstrated a nearly threefold increase in binding capacity at equivalent affinity when LRP was used. In addition, by adjusting the double bond conversion, we can choose to increase either the capacity or the affinity in highly cross-linked imprinted polymers, thus allowing the creation of imprinted polymers with tailorable binding parameters. Using free radical polymerization in the creation of polymer chains, as the template-monomer ratio increased, the average molecular weight of the polymer chains decreased despite a slight increase in the double bond conversion. Thus, the polymer chains formed were shorter but greater in number. Using LRP neutralized the effect of the template. The addition of chain transfer agent resulted in slow, uniform, simultaneous chain growth, resulting in the formation of longer more monodisperse chains. Reaction analysis revealed that propagation time was extended threefold in the formation of highly cross-linked polymers when LRP techniques were used. This delayed the transition to the diffusion-controlled stage of the reaction, which in turn led to the observed enhanced binding properties, decreased polydispersity in the chains, and a more homogeneous macromolecular architecture. Copyright © 2012 John Wiley & Sons, Ltd.

Polarizable polymer chain under external electric field: Effects of many-body electrostatic dipole correlations.

PubMed

Budkov, Yu A; Kolesnikov, A L

2016-11-01

We present a new simple self-consistent field theory of a polarizable flexible polymer chain under an external constant electric field with account for the many-body electrostatic dipole correlations. We show the effects of electrostatic dipole correlations on the electric-field-induced globule-coil transition. We demonstrate that only when the polymer chain is in the coil conformation, the electrostatic dipole correlations of monomers can be considered as pairwise. However, when the polymer chain is in a collapsed state, the dipole correlations have to be considered at the many-body level.

Efficient protein-repelling thin films regulated by chain mobility of low-Tg polymers with increased stability via crosslinking

NASA Astrophysics Data System (ADS)

Zhang, Jinghui; Huang, Zhiwei; Liu, Dan

2017-12-01

Polymer thin films are generally employed as coatings on implants to prevent protein adsorption. Polymer chain mobility and surface softness have been found to contribute to the protein resistance, but also bring film instability in a liquid protein medium. We investigated the protein resistance ability of three low-Tg polymers, including hydrophobic polymers polyisoprene (PI), poly(n-butyl methacrylate) (PnBMA) and hydrophilic polyethylene oxide (PEO), by overcoming the instability issue with crosslinking. We found that the Tgs of PI and PEO can be increased to around 0 °C after crosslinking. The remained strong chain mobility of both films can still resist protein adsorption regardless the hydrophobicity, yet greatly increases the film stability under an aqueous circumstance. The PnBMA film increased its Tg to around room temperature after crosslinking, which deteriorated the protein-resistance ability having the surface covered by BSA molecules. Our results support that the chain mobility of a polymer film plays an important role in resisting protein adsorption due to the increased entropy associated with more mobile polymer chains. By tune the degree of crosslinking, the stability of polymer in aqueous environment can be increased while the protein resistant ability can be remained. Our results provide a new strategy to design polymer materials for effective antifouling.

Annealed scaling for a charged polymer in dimensions two and higher

NASA Astrophysics Data System (ADS)

Berger, Q.; den Hollander, F.; Poisat, J.

2018-02-01

This paper considers an undirected polymer chain on {Z}d , d ≥slant 2 , with i.i.d. random charges attached to its constituent monomers. Each self-intersection of the polymer chain contributes an energy to the interaction Hamiltonian that is equal to the product of the charges of the two monomers that meet. The joint probability distribution for the polymer chain and the charges is given by the Gibbs distribution associated with the interaction Hamiltonian. The object of interest is the annealed free energy per monomer in the limit as the length n of the polymer chain tends to infinity. We show that there is a critical curve in the parameter plane spanned by the charge bias and the inverse temperature separating an extended phase from a collapsed phase. We derive the scaling of the critical curve for small and for large charge bias and the scaling of the annealed free energy for small inverse temperature. We argue that in the collapsed phase the polymer chain is subdiffusive, namely, on scale \

Doubly self-consistent field theory of grafted polymers under simple shear in steady state.

PubMed

Suo, Tongchuan; Whitmore, Mark D

2014-03-21

We present a generalization of the numerical self-consistent mean-field theory of polymers to the case of grafted polymers under simple shear. The general theoretical framework is presented, and then applied to three different chain models: rods, Gaussian chains, and finitely extensible nonlinear elastic (FENE) chains. The approach is self-consistent at two levels. First, for any flow field, the polymer density profile and effective potential are calculated self-consistently in a manner similar to the usual self-consistent field theory of polymers, except that the calculation is inherently two-dimensional even for a laterally homogeneous system. Second, through the use of a modified Brinkman equation, the flow field and the polymer profile are made self-consistent with respect to each other. For all chain models, we find that reasonable levels of shear cause the chains to tilt, but it has very little effect on the overall thickness of the polymer layer, causing a small decrease for rods, and an increase of no more than a few percent for the Gaussian and FENE chains. Using the FENE model, we also probe the individual bond lengths, bond correlations, and bond angles along the chains, the effects of the shear on them, and the solvent and bonded stress profiles. We find that the approximations needed within the theory for the Brinkman equation affect the bonded stress, but none of the other quantities.

Polymer dynamics: Floored by the rings

NASA Astrophysics Data System (ADS)

McLeish, Tom

2008-12-01

The tube model can explain how mutually entangled polymer chains move and interact, but it relies on the loose ends of chains to generate relaxation. Ring polymers have no ends - so how do they relax?

Use of side-chain for rational design of n-type diketopyrrolopyrrole-based conjugated polymers: what did we find out?

PubMed

Kanimozhi, Catherine; Yaacobi-Gross, Nir; Burnett, Edmund K; Briseno, Alejandro L; Anthopoulos, Thomas D; Salzner, Ulrike; Patil, Satish

2014-08-28

The primary role of substituted side chains in organic semiconductors is to increase their solubility in common organic solvents. In the recent past, many literature reports have suggested that the side chains play a critical role in molecular packing and strongly impact the charge transport properties of conjugated polymers. In this work, we have investigated the influence of side-chains on the charge transport behavior of a novel class of diketopyrrolopyrrole (DPP) based alternating copolymers. To investigate the role of side-chains, we prepared four diketopyrrolopyrrole-diketopyrrolopyrrole (DPP-DPP) conjugated polymers with varied side-chains and carried out a systematic study of thin film microstructure and charge transport properties in polymer thin-film transistors (PTFTs). Combining results obtained from grazing incidence X-ray diffraction (GIXD) and charge transport properties in PTFTs, we conclude side-chains have a strong influence on molecular packing, thin film microstructure, and the charge carrier mobility of DPP-DPP copolymers. However, the influence of side-chains on optical properties was moderate. The preferential "edge-on" packing and dominant n-channel behavior with exceptionally high field-effect electron mobility values of >1 cm(2) V(-1) s(-1) were observed by incorporating hydrophilic (triethylene glycol) and hydrophobic side-chains of alternate DPP units. In contrast, moderate electron and hole mobilities were observed by incorporation of branched hydrophobic side-chains. This work clearly demonstrates that the subtle balance between hydrophobicity and hydrophilicity induced by side-chains is a powerful strategy to alter the molecular packing and improve the ambipolar charge transport properties in DPP-DPP based conjugated polymers. Theoretical analysis supports the conclusion that the side-chains influence polymer properties through morphology changes, as there is no effect on the electronic properties in the gas phase. The exceptional electron mobility is at least partially a result of the strong intramolecular conjugation of the donor and acceptor as evidenced by the unusually wide conduction band of the polymer.

Macromolecular 'size' and 'hardness' drives structure in solvent-swollen blends of linear, cyclic, and star polymers.

PubMed

Gartner, Thomas E; Jayaraman, Arthi

2018-01-17

In this paper, we apply molecular simulation and liquid state theory to uncover the structure and thermodynamics of homopolymer blends of the same chemistry and varying chain architecture in the presence of explicit solvent species. We use hybrid Monte Carlo (MC)/molecular dynamics (MD) simulations in the Gibbs ensemble to study the swelling of ∼12 000 g mol -1 linear, cyclic, and 4-arm star polystyrene chains in toluene. Our simulations show that the macroscopic swelling response is indistinguishable between the various architectures and matches published experimental data for the solvent annealing of linear polystyrene by toluene vapor. We then use standard MD simulations in the NPT ensemble along with polymer reference interaction site model (PRISM) theory to calculate effective polymer-solvent and polymer-polymer Flory-Huggins interaction parameters (χ eff ) in these systems. As seen in the macroscopic swelling results, there are no significant differences in the polymer-solvent and polymer-polymer χ eff between the various architectures. Despite similar macroscopic swelling and effective interaction parameters between various architectures, the pair correlation function between chain centers-of-mass indicates stronger correlations between cyclic or star chains in the linear-cyclic blends and linear-star blends, compared to linear chain-linear chain correlations. Furthermore, we note striking similarities in the chain-level correlations and the radius of gyration of cyclic and 4-arm star architectures of identical molecular weight. Our results indicate that the cyclic and star chains are 'smaller' and 'harder' than their linear counterparts, and through comparison with MD simulations of blends of soft spheres with varying hardness and size we suggest that these macromolecular characteristics are the source of the stronger cyclic-cyclic and star-star correlations.

Geometric somersaults of a polymer chain through cyclic twisting motions

NASA Astrophysics Data System (ADS)

Yanao, Tomohiro; Hino, Taiko

2017-01-01

This study explores the significance of geometric angle shifts, which we call geometric somersaults, arising from cyclic twisting motions of a polymer chain. A five-bead polymer chain serves as a concise and minimal model of a molecular shaft throughout this study. We first show that this polymer chain can change its orientation about its longitudinal axis largely, e.g., 120∘, under conditions of zero total angular momentum by changing the two dihedral angles in a cyclic manner. This phenomenon is an example of the so-called "falling cat" phenomenon, where a falling cat undergoes a geometric somersault by changing its body shape under conditions of zero total angular momentum. We then extend the geometric somersault of the polymer chain to a noisy and viscous environment, where the polymer chain is steered by external driving forces. This extension shows that the polymer chain can achieve an orientation change keeping its total angular momentum and total external torque fluctuating around zero in a noisy and viscous environment. As an application, we argue that the geometric somersault of the polymer chain by 120∘ may serve as a prototypical and coarse-grained model for the rotary motion of the central shaft of ATP synthase (FOF1 -ATPase). This geometric somersault is in clear contrast to the standard picture for the rotary motion of the central shaft as a rigid body, which generally incurs nonzero total angular momentum and nonzero total external torque. The power profile of the geometric somersault implies a preliminary mechanism for elastic power transmission. The results of this study may be of fundamental interest in twisting and rotary motions of biomolecules.

Equivalence of chain conformations in the surface region of a polymer melt and a single Gaussian chain under critical conditions.

PubMed

Skvortsov, A M; Leermakers, F A M; Fleer, G J

2013-08-07

In the melt polymer conformations are nearly ideal according to Flory's ideality hypothesis. Silberberg generalized this statement for chains in the interfacial region. We check the Silberberg argument by analyzing the conformations of a probe chain end-grafted at a solid surface in a sea of floating free chains of concentration φ by the self-consistent field (SCF) method. Apart from the grafting, probe chain and floating chains are identical. Most of the results were obtained for a standard SCF model with freely jointed chains on a six-choice lattice, where immediate step reversals are allowed. A few data were generated for a five-choice lattice, where such step reversals are forbidden. These coarse-grained models describe the equilibrium properties of flexible atactic polymer chains at the scale of the segment length. The concentration was varied over the whole range from φ = 0 (single grafted chain) to φ = 1 (probe chain in the melt). The number of contacts with the surface, average height of the free end and its dispersion, average loop and train length, tail size distribution, end-point and overall segment distributions were calculated for a grafted probe chain as a function of φ, for several chain lengths and substrate∕polymer interactions, which were varied from strong repulsion to strong adsorption. The computations show that the conformations of the probe chain in the melt do not depend on substrate∕polymer interactions and are very similar to the conformations of a single end-grafted chain under critical conditions, and can thus be described analytically. When the substrate∕polymer interaction is fixed at the value corresponding to critical conditions, all equilibrium properties of a probe chain are independent of φ, over the whole range from a dilute solution to the melt. We believe that the conformations of all flexible chains in the surface region of the melt are close to those of an appropriate single chain in critical conditions, provided that one end of the single chain is fixed at the same point as a chain in the melt.

Structure-induced switching of interpolymer adhesion at a solid–polymer melt interface

DOE PAGES

Jiang, Naisheng; Sen, Mani; Zeng, Wenduo; ...

2018-01-11

In this paper, we report a link between the interfacial structure and adhesive property of homopolymer chains physically adsorbed (i.e., via physisorption) onto solids. Polyethylene oxide (PEO) was used as a model and two different chain conformations of the adsorbed polymer were created on silicon substrates via the well-established Guiselin's approach: “flattened chains” which lie flat on the solid and are densely packed, and “loosely adsorbed polymer chains” which form bridges jointing up nearby empty sites on the solid surface and cover the flattened chains. We investigated the adhesion properties of the two different adsorbed chains using a custom-built adhesionmore » testing device. Bilayers of a thick PEO overlayer on top of the flattened chains or loosely adsorbed chains were subjected to the adhesion test. The results revealed that the flattened chains do not show any adhesion even with the chemically identical free polymer on top, while the loosely adsorbed chains exhibit adhesion. Neutron reflectivity experiments corroborated that the difference in the interfacial adhesion is not attributed to the interfacial brodening at the free polymer–adsorbed polymer interface. Instead, coarse-grained molecular dynamics simulation results suggest that the tail parts of the loosely adsorbed chains act as “connector molecules”, bridging the free chains and substrate surface and improving the interfacial adhesion. Finally, these findings not only shed light on the structure–property relationship at the interface, but also provide a novel approach for developing sticking/anti-sticking technologies through precise control of the interfacial polymer nanostructures.« less

Synthesis of diketopyrrolopyrrole-based polymers with polydimethylsiloxane side chains and their application in organic field-effect transistors

NASA Astrophysics Data System (ADS)

Ohnishi, Inori; Hashimoto, Kazuhito; Tajima, Keisuke

2018-03-01

Linear polydimethylsiloxane (PDMS) was investigated as a solubilizing group for π-conjugated polymers with the aim of combining high solubility in organic solvents with the molecular packing in solid films that is advantageous for charge transport. Diketopyrrolopyrrole-based copolymers with different contents and substitution patterns of the PDMS side chains were synthesized and evaluated for application in organic field-effect transistors. The PDMS side chains greatly increased the solubility of the polymers and led to shorter d-spacings of the π-stacking in the thin films compared with polymers containing conventional branched alkyl side chains.

Microscopic Chain Motion in Polymer Nanocomposites with Dynamically Asymmetric Interphases

PubMed Central

Senses, Erkan; Faraone, Antonio; Akcora, Pinar

2016-01-01

Dynamics of the interphase region between matrix and bound polymers on nanoparticles is important to understand the macroscopic rheological properties of nanocomposites. Here, we present neutron scattering investigations on nanocomposites with dynamically asymmetric interphases formed by a high-glass transition temperature polymer, poly(methyl methacrylate), adsorbed on nanoparticles and a low-glass transition temperature miscible matrix, poly(ethylene oxide). By taking advantage of selective isotope labeling of the chains, we studied the role of interfacial polymer on segmental and collective dynamics of the matrix chains from subnanoseconds to 100 nanoseconds. Our results show that the Rouse relaxation remains unchanged in a weakly attractive composite system while the dynamics significantly slows down in a strongly attractive composite. More importantly, the chains disentangle with a remarkable increase of the reptation tube size when the bound polymer is vitreous. The glassy and rubbery states of the bound polymer as temperature changes underpin the macroscopic stiffening of nanocomposites. PMID:27457056

Investigation of the adsorption of polymer chains on amine-functionalized double-walled carbon nanotubes.

PubMed

Ansari, R; Ajori, S; Rouhi, S

2015-12-01

Molecular dynamics (MD) simulations were used to study the adsorption of different polymer chains on functionalized double-walled carbon nanotubes (DWCNTs). The nanotubes were functionalized with two different amines: NH2 (a small amine) and CH2-NH2 (a large amine). Considering three different polymer chains, all with the same number of atoms, the effect of polymer type on the polymer-nanotube interaction was studied. In general, it was found that covalent functionalization considerably improved the polymer-DWCNT interaction. By comparing the results obtained with different polymer chains, it was observed that, unlike polyethylene and polyketone, poly(styrene sulfonate) only weakly interacts with the functionalized DWCNTs. Accordingly, the smallest radius of gyration was obtained with adsorbed poly(styrene sulfonate). It was also observed that the DWCNTs functionalized with the large amine presented more stable interactions with polyketone and poly(styrene sulfonate) than with polyethylene, whereas the DWCNTs functionalized with the small amine showed better interfacial noncovalent bonding with polyethylene.

High thermal conductivity in electrostatically engineered amorphous polymers

PubMed Central

Shanker, Apoorv; Li, Chen; Kim, Gun-Ho; Gidley, David; Pipe, Kevin P.; Kim, Jinsang

2017-01-01

High thermal conductivity is critical for many applications of polymers (for example, packaging of light-emitting diodes), in which heat must be dissipated efficiently to maintain the functionality and reliability of a system. Whereas uniaxially extended chain morphology has been shown to significantly enhance thermal conductivity in individual polymer chains and fibers, bulk polymers with coiled and entangled chains have low thermal conductivities (0.1 to 0.4 W m−1 K−1). We demonstrate that systematic ionization of a weak anionic polyelectrolyte, polyacrylic acid (PAA), resulting in extended and stiffened polymer chains with superior packing, can significantly enhance its thermal conductivity. Cross-plane thermal conductivity in spin-cast amorphous films steadily grows with PAA degree of ionization, reaching up to ~1.2 W m−1 K−1, which is on par with that of glass and about six times higher than that of most amorphous polymers, suggesting a new unexplored molecular engineering strategy to achieve high thermal conductivities in amorphous bulk polymers. PMID:28782022

The influence of polymer architectures on the dewetting behavior of thin polymer films: from linear chains to ring chains.

PubMed

Wang, Lina; Xu, Lin; Liu, Binyuan; Shi, Tongfei; Jiang, Shichun; An, Lijia

2017-05-03

The dewetting behavior of ring polystyrene (RPS) film and linear polystyrene (LPS) film on silanized Si substrates with different grafting densities and PDMS substrate was investigated. Results showed that polymer architectures greatly influenced the dewetting behavior of the thin polymer film. On the silanized Si substrate with 69% grafting density, RPS chains exhibited stronger adsorption compared with LPS chains, and as a result the wetting layer formed more easily. For LPS films, with a decreased annealing temperature, the stability of the polymer film changed from non-slip dewetting via apparent slip dewetting to apparently stable. However, for RPS films, the polymer film stability switched from apparent slip dewetting to apparently stable. On the silanized Si substrate with 94% grafting density, the chain adsorption became weaker and the dewetting processes were faster than that on the substrate with 69% grafting density at the same experimental temperature for both the LPS and RPS films. Moreover, on the PDMS substrate, LPS films always showed non-slip dewetting, while the dewetting kinetics of RPS films switched from non-slip dewetting to slip dewetting behaviour. Forming the wetting layer strongly influenced the stability and dewetting behavior of the thin polymer films.

Lattice model of linear telechelic polymer melts. II. Influence of chain stiffness on basic thermodynamic properties

DOE Office of Scientific and Technical Information (OSTI.GOV)

Xu, Wen-Sheng, E-mail: wsxu@uchicago.edu; Freed, Karl F., E-mail: freed@uchicago.edu; Department of Chemistry, The University of Chicago, Chicago, Illinois 60637

2015-07-14

The lattice cluster theory (LCT) for semiflexible linear telechelic melts, developed in Paper I, is applied to examine the influence of chain stiffness on the average degree of self-assembly and the basic thermodynamic properties of linear telechelic polymer melts. Our calculations imply that chain stiffness promotes self-assembly of linear telechelic polymer melts that assemble on cooling when either polymer volume fraction ϕ or temperature T is high, but opposes self-assembly when both ϕ and T are sufficiently low. This allows us to identify a boundary line in the ϕ-T plane that separates two regions of qualitatively different influence of chainmore » stiffness on self-assembly. The enthalpy and entropy of self-assembly are usually treated as adjustable parameters in classical Flory-Huggins type theories for the equilibrium self-assembly of polymers, but they are demonstrated here to strongly depend on chain stiffness. Moreover, illustrative calculations for the dependence of the entropy density of linear telechelic polymer melts on chain stiffness demonstrate the importance of including semiflexibility within the LCT when exploring the nature of glass formation in models of linear telechelic polymer melts.« less

Enthalpic and Entropic Competition in Blends of Self-Suspended Hairy Nanoparticles

NASA Astrophysics Data System (ADS)

Choudhury, Snehashis; Agrawal, Akanksha; Archer, Lynden

Self-suspended hairy nanoparticles, where polymer chains are grafted onto nanoparticles, have attracted significant recent attention. These materials have been reported to manifest several interesting phenomena like thermal jamming, slowing-down of polymer chain dynamics, as well as small-strain stress overshoots during start-up of steady shear. The entropic penalty on tethered polymers produced by the requirement that they fill the space between the nanoparticle cores explain most of these behaviors. Here, we show that the entropic attraction between tethered polymer chains can be manipulated in mixtures of hairy nanoparticles using different polymer chemistry to design materials with unusual characteristics. Specifically, the degree of interpenetration of polymer chains can be controlled by tuning their interaction parameter (χ) . For SiO2-PEG/SiO2-PMMA blends, oscillatory rheological measurements show that the plateau modulus and yielding energy are significantly increased, while an opposite effect is seen with SiO2-PEG/SiO2-PI blends. More subtle effects of this enthalpy-entropy competition are well captured in Dielectric Spectroscopy measurements and SAXS experiments that can be used to quantify the degree of stretch and interdigitation of polymer chains.

ONR Far East Scientific Information Bulletin

DTIC Science & Technology

1990-09-01

In bone, grafting onto a polymer chain, inter- continuous processes, such as reactive extru- chain reactions, formation of interpenetrat- sion and...reaction kinetics, rheology, and side- and end-chain grafting , homopolymer transport phenomena occurring during REX. chain coupling, polymer...the Grafting reactions yield block or graft coupling species becomes a part of the chain, copolymers. Polyethylene, polypropylene, or by

Supramolecular Polymers Based on Non-Coplanar AAA-DDD Hydrogen-Bonded Complexes.

PubMed

Mendez, Iamnica J Linares; Wang, Hong-Bo; Yuan, Ying-Xue; Wisner, James A

2018-03-01

Non-coplanar triple-hydrogen-bond arrays are connected as telechelic groups to alkyl chains and their properties as AA/BB type supramolecular polymers are examined. Viscosity studies at three temperatures are used to study the ring-chain equilibrium and determine the critical concentrations where polymer chains are formed. It is observed that neither the temperature range studied nor the alkyl chain length of one component significantly affect the polymerization properties in this system. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Doubly self-consistent field theory of grafted polymers under simple shear in steady state

DOE Office of Scientific and Technical Information (OSTI.GOV)

Suo, Tongchuan; Whitmore, Mark D., E-mail: mark-whitmore@umanitoba.ca

2014-03-21

We present a generalization of the numerical self-consistent mean-field theory of polymers to the case of grafted polymers under simple shear. The general theoretical framework is presented, and then applied to three different chain models: rods, Gaussian chains, and finitely extensible nonlinear elastic (FENE) chains. The approach is self-consistent at two levels. First, for any flow field, the polymer density profile and effective potential are calculated self-consistently in a manner similar to the usual self-consistent field theory of polymers, except that the calculation is inherently two-dimensional even for a laterally homogeneous system. Second, through the use of a modified Brinkmanmore » equation, the flow field and the polymer profile are made self-consistent with respect to each other. For all chain models, we find that reasonable levels of shear cause the chains to tilt, but it has very little effect on the overall thickness of the polymer layer, causing a small decrease for rods, and an increase of no more than a few percent for the Gaussian and FENE chains. Using the FENE model, we also probe the individual bond lengths, bond correlations, and bond angles along the chains, the effects of the shear on them, and the solvent and bonded stress profiles. We find that the approximations needed within the theory for the Brinkman equation affect the bonded stress, but none of the other quantities.« less

Approaching Intra- and Interchain Charge Transport of Conjugated Polymers Facilely by Topochemical Polymerized Single Crystals.

PubMed

Yao, Yifan; Dong, Huanli; Liu, Feng; Russell, Thomas P; Hu, Wenping

2017-08-01

Charge transport of small molecules is measured well with scanning tunneling microscopy, conducting atomic force microscopy, break junction, nanopore, and covalently bridging gaps. However, the manipulation and measurement of polymer chains remain a long-standing fundamental issue in conjugated polymers and full of challenge since conjugated polymers are naturally disordered materials. Here, a fundamental breakthrough in generating high-quality conjugated-polymer nanocrystals with extended conjugation and exceptionally high degrees of order using a surface-supported topochemical polymerization method is demonstrated. In the crystal the conjugated-polymer chains are extended along the long axis of the crystal with the side chains perpendicular to the long axis. Devices with conducting channels along the polymer chains show efficient charge transport, nearly two orders of magnitude greater than the interchain charge transport along the π-π stacking direction. This is the first example to clarify intra- and interchain charge transport based on an individual single crystal of conjugated polymers, and demonstrate the importance of intrachain charge transport in plastic electronics. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Multiple dynamic regimes in colloid-polymer dispersions: New insight using X-ray photon correlation spectroscopy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Srivastava, Sunita; Kishore, Suhasini; Narayanan, Suresh

We present an X-ray photon correlation spectros- copy (XPCS) study of dynamic transitions in an anisotropic colloid-polymer dispersion with multiple arrested states. The results provide insight into the mechanism for formation of repulsive glasses, attractive glasses, and networked gels of col- loids with weakly adsorbing polymer chains. In the presence of adsorbing polymer chains, we observe three distinct regimes: a state with slow dynamics consisting of finite particles and clusters, for which interparticle interactions are predominantly repulsive; a second dynamic regime occurring above the satu- ration concentration of added polymer, in which small clusters of nanoparticles form via a short-rangemore » depletion attraction; and a third regime above the overlap concentration in which dynamics of clusters are independent of polymer chain length. The observed complex dynamic state diagram is primarily gov- erned by the structural reorganization of a nanoparticle cluster and polymer chains at the nanoparticle-polymer surface and in the concentrated medium, which in turn controls the dynamics of the dispersion« less

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

PubMed

Gauthier, Marc A; Klok, Harm-Anton

2008-06-21

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

Energy transfer in PPV-based conjugated polymers: a defocused widefield fluorescence microscopy study.

PubMed

Hooley, E N; Tilley, A J; White, J M; Ghiggino, K P; Bell, T D M

2014-04-21

Both pendant and main chain conjugated MEH-PPV based polymers have been studied at the level of single chains using confocal and widefield fluorescence microscopy techniques. In particular, defocused widefield fluorescence is applied to reveal the extent of energy transfer in these polymers by identifying whether they act as single emitters. For main chain conjugated MEH-PPV, molecular weight and the surrounding matrix play a primary role in determining energy transport processes and whether single emitter behaviour is observed. Surprisingly in polymers with a saturated backbone but containing the same pendant MEH-PPV oligomer on each repeating unit, intra-chain energy transfer to a single emitter is also apparent. The results imply there is chromophore heterogeneity that can facilitate energy funneling to the emitting site. Both main chain conjugated and pendant MEH-PPV polymers exhibit changes in orientation of the emission dipole during a fluorescence trajectory of many seconds, whereas a model MEH-PPV oligomer does not. The results suggest that, in the polymers, the nature of the emitting chromophores can change during the time trajectory.

Molecular engineered conjugated polymer with high thermal conductivity

PubMed Central

Song, Bai; Lee, Elizabeth M. Y.; Gleason, Karen K.

2018-01-01

Traditional polymers are both electrically and thermally insulating. The development of electrically conductive polymers has led to novel applications such as flexible displays, solar cells, and wearable biosensors. As in the case of electrically conductive polymers, the development of polymers with high thermal conductivity would open up a range of applications in next-generation electronic, optoelectronic, and energy devices. Current research has so far been limited to engineering polymers either by strong intramolecular interactions, which enable efficient phonon transport along the polymer chains, or by strong intermolecular interactions, which enable efficient phonon transport between the polymer chains. However, it has not been possible until now to engineer both interactions simultaneously. We report the first realization of high thermal conductivity in the thin film of a conjugated polymer, poly(3-hexylthiophene), via bottom-up oxidative chemical vapor deposition (oCVD), taking advantage of both strong C=C covalent bonding along the extended polymer chain and strong π-π stacking noncovalent interactions between chains. We confirm the presence of both types of interactions by systematic structural characterization, achieving a near–room temperature thermal conductivity of 2.2 W/m·K, which is 10 times higher than that of conventional polymers. With the solvent-free oCVD technique, it is now possible to grow polymer films conformally on a variety of substrates as lightweight, flexible heat conductors that are also electrically insulating and resistant to corrosion. PMID:29670943

Shear-induced desorption of isolated polymer molecules from a planar wall

NASA Astrophysics Data System (ADS)

Dutta, Sarit; Dorfman, Kevin; Kumar, Satish

2014-03-01

Shear-induced desorption of isolated polymer molecules is studied using Brownian dynamics simulations. The polymer molecules are modeled as freely jointed bead-spring chains interacting with a planar wall via a short-range potential. The simulations include both intrachain and chain-wall hydrodynamic interactions. Shear flow is found to cause chain flattening, resulting at low shear rates in an increased fraction of chain segments bound to the wall. However, above a critical shear rate the chains desorb completely. The desorption process is nucleated by random protrusions in the shear gradient direction which evolve under the combined effect of drag, hydrodynamic interaction, and vorticity-induced rotation, and subsequently lead to recapture. Above the critical shear rate, these protrusions grow in length until the entire chain is peeled off the wall. For free-draining chains, the protrusions are not sustained and no desorption is observed even at shear rates much higher than the critical value. These simulations can help in interpreting experiments on shear-induced desorption of polymer films and brushes.

Selective Template Wetting Routes to Hierarchical Polymer Films: Polymer Nanotubes from Phase-Separated Films via Solvent Annealing.

PubMed

Ko, Hao-Wen; Cheng, Ming-Hsiang; Chi, Mu-Huan; Chang, Chun-Wei; Chen, Jiun-Tai

2016-03-01

We demonstrate a novel wetting method to prepare hierarchical polymer films with polymer nanotubes on selective regions. This strategy is based on the selective wetting abilities of polymer chains, annealed in different solvent vapors, into the nanopores of porous templates. Phase-separated films of polystyrene (PS) and poly(methyl methacrylate) (PMMA), two commonly used polymers, are prepared as a model system. After anodic aluminum oxide (AAO) templates are placed on the films, the samples are annealed in vapors of acetic acid, in which the PMMA chains are swollen and wet the nanopores of the AAO templates selectively. As a result, hierarchical polymer films containing PMMA nanotubes can be obtained after the AAO templates are removed. The distribution of the PMMA nanotubes of the hierarchical polymer films can also be controlled by changing the compositions of the polymer blends. This work not only presents a novel method to fabricate hierarchical polymer films with polymer nanotubes on selective regions, but also gives a deeper understanding in the selective wetting ability of polymer chains in solvent vapors.

Statistical properties of multi-theta polymer chains

NASA Astrophysics Data System (ADS)

Uehara, Erica; Deguchi, Tetsuo

2018-04-01

We study statistical properties of polymer chains with complex structures whose chemical connectivities are expressed by graphs. The multi-theta curve of m subchains with two branch points connected by them is one of the simplest graphs among those graphs having closed paths, i.e. loops. We denoted it by θm , and for m  =  2 it is given by a ring. We derive analytically the pair distribution function and the scattering function for the θm -shaped polymer chains consisting of m Gaussian random walks of n steps. Surprisingly, it is shown rigorously that the mean-square radius of gyration for the Gaussian θm -shaped polymer chain does not depend on the number m of subchains if each subchain has the same fixed number of steps. For m  =  3 we show the Kratky plot for the theta-shaped polymer chain consisting of hard cylindrical segments by the Monte-Carlo method including reflection at trivalent vertices.

Fine-tuning blend morphology via alkylthio side chain engineering towards high performance non-fullerene polymer solar cells

NASA Astrophysics Data System (ADS)

Li, Ling; Feng, Liuliu; Yuan, Jun; Peng, Hongjian; Zou, Yingping; Li, Yongfang

2018-03-01

Two medium bandgap polymers (ffQx-TS1, ffQx-TS2) were designed and synthesized to investigate the influence of different alkylthio side chain on the morphology and photovoltaic performance of non-fullerene polymer solar cells (PSCs). Both polymers exhibit similar molecular weights and comparable the highest occupied molecular orbital (HOMO) energy level. However, the polymer with straight alkylthio chain delivers a root-mean-square (RMS) of 0.86 nm, which is slightly lower than that with branched chain (1.40 nm). The lower RMS benefits the ohmic contact between the active lay and interface layer, thus enhanced short circuit current (Jsc) (from 13.54 mA cm-1 to 15.25 mA cm-1) could be obtained. Due to the enhancement of Jsc, better power conversion efficiency (PCE) of 7.69% for ffQx-TS2 could be realized. These results indicated that alkylthio side chain engineering is a promising method to improve photovoltaic performance.

Compartmentalization Technologies via Self-Assembly and Cross-Linking of Amphiphilic Random Block Copolymers in Water.

PubMed

Matsumoto, Mayuko; Terashima, Takaya; Matsumoto, Kazuma; Takenaka, Mikihito; Sawamoto, Mitsuo

2017-05-31

Orthogonal self-assembly and intramolecular cross-linking of amphiphilic random block copolymers in water afforded an approach to tailor-make well-defined compartments and domains in single polymer chains and nanoaggregates. For a double compartment single-chain polymer, an amphiphilic random block copolymer bearing hydrophilic poly(ethylene glycol) (PEG) and hydrophobic dodecyl, benzyl, and olefin pendants was synthesized by living radical polymerization (LRP) and postfunctionalization; the dodecyl and benzyl units were incorporated into the different block segments, whereas PEG pendants were statistically attached along a chain. The copolymer self-folded via the orthogonal self-assembly of hydrophobic dodecyl and benzyl pendants in water, followed by intramolecular cross-linking, to form a single-chain polymer carrying double yet distinct hydrophobic nanocompartments. A single-chain cross-linked polymer with a chlorine terminal served as a globular macroinitiator for LRP to provide an amphiphilic tadpole macromolecule comprising a hydrophilic nanoparticle and a hydrophobic polymer tail; the tadpole thus self-assembled into multicompartment aggregates in water.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jiang, Naisheng; Sen, Mani; Zeng, Wenduo

In this paper, we report a link between the interfacial structure and adhesive property of homopolymer chains physically adsorbed (i.e., via physisorption) onto solids. Polyethylene oxide (PEO) was used as a model and two different chain conformations of the adsorbed polymer were created on silicon substrates via the well-established Guiselin's approach: “flattened chains” which lie flat on the solid and are densely packed, and “loosely adsorbed polymer chains” which form bridges jointing up nearby empty sites on the solid surface and cover the flattened chains. We investigated the adhesion properties of the two different adsorbed chains using a custom-built adhesionmore » testing device. Bilayers of a thick PEO overlayer on top of the flattened chains or loosely adsorbed chains were subjected to the adhesion test. The results revealed that the flattened chains do not show any adhesion even with the chemically identical free polymer on top, while the loosely adsorbed chains exhibit adhesion. Neutron reflectivity experiments corroborated that the difference in the interfacial adhesion is not attributed to the interfacial brodening at the free polymer–adsorbed polymer interface. Instead, coarse-grained molecular dynamics simulation results suggest that the tail parts of the loosely adsorbed chains act as “connector molecules”, bridging the free chains and substrate surface and improving the interfacial adhesion. Finally, these findings not only shed light on the structure–property relationship at the interface, but also provide a novel approach for developing sticking/anti-sticking technologies through precise control of the interfacial polymer nanostructures.« less

Three d10 coordination polymers assembled from 3,5-bis(imidazole-1-yl)pyridine and different polycarboxylates: Syntheses, structures and luminescence properties

NASA Astrophysics Data System (ADS)

Pan, Jie; Zhang, Di; Xue, Zhen-Zhen; Wei, Li; Han, Song-De; Wang, Guo-Ming

2017-11-01

Three novel Zn(II)/Cd(II) coordination polymers, [Cd2(bip)2(m-bdc)2(H2O)2·3H2O]n (1), [Zn2(bip)2(p-bdc)2·2.5H2O]n (2) and [Zn(bip) (p-bdc)·3H2O]n (3), where bip = 3,5-bis(imidazole-1-yl)pyridine, m-H2bdc = 1,3-benzenedicarboxylic acid, p-H2bdc = 1,4-benzenedicarboxylic acid, have been successfully synthesized under solvothermal conditions. The linkage of different ligands with Cd(II) ions in compound 1 affords a (3,5)-connected layer. Furthermore, 2D→3D parallel polycatenation occurs wherein the layers are polycatenated with the adjacent two parallel layers to form a 3D framework. In 2 and 3, the polycarboxylates act as pillars to combine the metal-bip chains, yielding the layered structures. These 2D networks are extended to the final 3D supramolecular architectures by π-π stacking interactions. The results show that bip can act as a versatile building block for the construction of various coordination polymers. Moreover, the fluorescent properties of 1-3 in the solid state at room temperature have been investigated.

Side Chain Degradable Cationic-Amphiphilic Polymers with Tunable Hydrophobicity Show in Vivo Activity.

PubMed

Uppu, Divakara S S M; Samaddar, Sandip; Hoque, Jiaul; Konai, Mohini M; Krishnamoorthy, Paramanandham; Shome, Bibek R; Haldar, Jayanta

2016-09-12

Cationic-amphiphilic antibacterial polymers with optimal amphiphilicity generally target the bacterial membranes instead of mammalian membranes. To date, this balance has been achieved by varying the cationic charge or side chain hydrophobicity in a variety of cationic-amphiphilic polymers. Optimal hydrophobicity of cationic-amphiphilic polymers has been considered as the governing factor for potent antibacterial activity yet minimal mammalian cell toxicity. However, the concomitant role of hydrogen bonding and hydrophobicity with constant cationic charge in the interactions of antibacterial polymers with bacterial membranes is not understood. Also, degradable polymers that result in nontoxic degradation byproducts offer promise as safe antibacterial agents. Here we show that amide- and ester (degradable)-bearing cationic-amphiphilic polymers with tunable side chain hydrophobicity can modulate antibacterial activity and cytotoxicity. Our results suggest that an amide polymer can be a potent antibacterial agent with lower hydrophobicity whereas the corresponding ester polymer needs a relatively higher hydrophobicity to be as effective as its amide counterpart. Our studies reveal that at higher hydrophobicities both amide and ester polymers have similar profiles of membrane-active antibacterial activity and mammalian cell toxicity. On the contrary, at lower hydrophobicities, amide and ester polymers are less cytotoxic, but the former have potent antibacterial and membrane activity compared to the latter. Incorporation of amide and ester moieties made these polymers side chain degradable, with amide polymers being more stable than the ester polymers. Further, the polymers are less toxic, and their degradation byproducts are nontoxic to mice. More importantly, the optimized amide polymer reduces the bacterial burden of burn wound infections in mice models. Our design introduces a new strategy of interplay between the hydrophobic and hydrogen bonding interactions keeping constant cationic charge density for developing potent membrane-active antibacterial polymers with minimal toxicity to mammalian cells.

Computational Modeling of Hydroxypropyl-Methylcellulose Acetate Succinate (HPMCAS) and Phenytoin Interactions: A Systematic Coarse-Graining Approach.

PubMed

Huang, Wenjun; Mandal, Taraknath; Larson, Ronald G

2017-03-06

We present coarse-grained (CG) force fields for hydroxypropyl-methylcellulose acetate succinate (HPMCAS) polymers and the drug molecule phenytoin using a bead/stiff spring model, with each bead representing a HPMCAS monomer or monomer side group (hydroxypropyl acetyl, acetyl, or succinyl) or a single phenytoin ring. We obtain the bonded and nonbonded interaction parameters in our CG model using the RDFs from atomistic simulations of short HPMCAS model oligomers (20-mer) and atomistic simulations of phenytoin molecules. The nonbonded interactions are modeled using a LJ 12-6 potential, with separate parameters for each monomer substitution type, which allows heterogeneous polymer chains to be modeled. The cross interaction terms between the polymer and phenytoin CG beads are obtained explicitly from atomistic level polymer-phenytoin simulations, rather than from mixing rules. We study the solvation behavior of 50-mer and 100-mer polymer chains and find chain-length-dependent aggregation. We also compare the phenytoin CG force field developed in this work with that in Mandal et al. (Soft Matter, 2016, 12, 8246-8255) and conclude both are suitable for studying the interaction between polymer and drug in solvated solid dispersion formulation, in the absence of drug crystallization. Finally, we present simulations of heterogeneous HPMCAS model polymer chains and phenytoin molecules. Polymer and drug form a complex in a short period of simulation time due to strong intermolecular interactions. Moreover, the protonated polymer chains are more effective than deprotonated ones in inhibiting the drug aggregation in the polymer-drug complex.

Polymer ultrapermeability from the inefficient packing of 2D chains

NASA Astrophysics Data System (ADS)

Rose, Ian; Bezzu, C. Grazia; Carta, Mariolino; Comesaña-Gándara, Bibiana; Lasseuguette, Elsa; Ferrari, M. Chiara; Bernardo, Paola; Clarizia, Gabriele; Fuoco, Alessio; Jansen, Johannes C.; Hart, Kyle E.; Liyana-Arachchi, Thilanga P.; Colina, Coray M.; McKeown, Neil B.

2017-09-01

The promise of ultrapermeable polymers, such as poly(trimethylsilylpropyne) (PTMSP), for reducing the size and increasing the efficiency of membranes for gas separations remains unfulfilled due to their poor selectivity. We report an ultrapermeable polymer of intrinsic microporosity (PIM-TMN-Trip) that is substantially more selective than PTMSP. From molecular simulations and experimental measurement we find that the inefficient packing of the two-dimensional (2D) chains of PIM-TMN-Trip generates a high concentration of both small (<0.7 nm) and large (0.7-1.0 nm) micropores, the former enhancing selectivity and the latter permeability. Gas permeability data for PIM-TMN-Trip surpass the 2008 Robeson upper bounds for O2/N2, H2/N2, CO2/N2, H2/CH4 and CO2/CH4, with the potential for biogas purification and carbon capture demonstrated for relevant gas mixtures. Comparisons between PIM-TMN-Trip and structurally similar polymers with three-dimensional (3D) contorted chains confirm that its additional intrinsic microporosity is generated from the awkward packing of its 2D polymer chains in a 3D amorphous solid. This strategy of shape-directed packing of chains of microporous polymers may be applied to other rigid polymers for gas separations.

Engineering live cell surfaces with functional polymers via cytocompatible controlled radical polymerization

NASA Astrophysics Data System (ADS)

Niu, Jia; Lunn, David J.; Pusuluri, Anusha; Yoo, Justin I.; O'Malley, Michelle A.; Mitragotri, Samir; Soh, H. Tom; Hawker, Craig J.

2017-06-01

The capability to graft synthetic polymers onto the surfaces of live cells offers the potential to manipulate and control their phenotype and underlying cellular processes. Conventional grafting-to strategies for conjugating preformed polymers to cell surfaces are limited by low polymer grafting efficiency. Here we report an alternative grafting-from strategy for directly engineering the surfaces of live yeast and mammalian cells through cell surface-initiated controlled radical polymerization. By developing cytocompatible PET-RAFT (photoinduced electron transfer-reversible addition-fragmentation chain-transfer polymerization), synthetic polymers with narrow polydispersity (Mw/Mn < 1.3) could be obtained at room temperature in 5 minutes. This polymerization strategy enables chain growth to be initiated directly from chain-transfer agents anchored on the surface of live cells using either covalent attachment or non-covalent insertion, while maintaining high cell viability. Compared with conventional grafting-to approaches, these methods significantly improve the efficiency of grafting polymer chains and enable the active manipulation of cellular phenotypes.

Direct observation of single flexible polymers using single stranded DNA†

PubMed Central

Brockman, Christopher; Kim, Sun Ju

2012-01-01

Over the last 15 years, double stranded DNA (dsDNA) has been used as a model polymeric system for nearly all single polymer dynamics studies. However, dsDNA is a semiflexible polymer with markedly different molecular properties compared to flexible chains, including synthetic organic polymers. In this work, we report a new system for single polymer studies of flexible chains based on single stranded DNA (ssDNA). We developed a method to synthesize ssDNA for fluorescence microscopy based on rolling circle replication, which generates long strands (>65 kb) of ssDNA containing “designer” sequences, thereby preventing intramolecular base pair interactions. Polymers are synthesized to contain amine-modified bases randomly distributed along the backbone, which enables uniform labelling of polymer chains with a fluorescent dye to facilitate fluorescence microscopy and imaging. Using this approach, we synthesized ssDNA chains with long contour lengths (>30 μm) and relatively low dye loading ratios (~1 dye per 100 bases). In addition, we used epifluorescence microscopy to image single ssDNA polymer molecules stretching in flow in a microfluidic device. Overall, we anticipate that ssDNA will serve as a useful model system to probe the dynamics of polymeric materials at the molecular level. PMID:22956981

Crazing of nanocomposites with polymer-tethered nanoparticles

DOE PAGES

Meng, Dong; Kumar, Sanat K.; Ge, Ting; ...

2016-09-07

The crazing behavior of polymer nanocomposites formed by blending polymer grafted nanoparticles with an entangled polymer melt is studied by molecular dynamics simulations. We focus on the three key differences in the crazing behavior of a composite relative to the pure homopolymer matrix, namely, a lower yield stress, a smaller extension ratio, and a grafted chain length dependent failure stress. The yield behavior is found to be mostly controlled by the local nanoparticle-grafted polymer interfacial energy, with the grafted polymer-polymer matrix interfacial structure being of little to no relevance. Increasing the attraction between nanoparticle core and the grafted polymer inhibitsmore » void nucleation and leads to a higher yield stress. In the craze growth regime, the presence of “grafted chain” sections of ≈100 monomers alters the mechanical response of composite samples, giving rise to smaller extension ratios and higher drawing stresses than for the homopolymer matrix. As a result, the dominant failure mechanism of composite samples depends strongly on the length of the grafted chains, with disentanglement being the dominant mechanism for short chains, while bond breaking is the failure mode for chain lengths >10N e, where N e is the entanglement length.« less

Communication: Polarizable polymer chain under external electric field in a dilute polymer solution.

PubMed

Budkov, Yu A; Kolesnikov, A L; Kiselev, M G

2015-11-28

We study the conformational behavior of polarizable polymer chain under an external homogeneous electric field within the Flory type self-consistent field theory. We consider the influence of electric field on the polymer coil as well as on the polymer globule. We show that when the polymer chain conformation is a coil, application of external electric field leads to its additional swelling. However, when the polymer conformation is a globule, a sufficiently strong field can induce a globule-coil transition. We show that such "field-induced" globule-coil transition at the sufficiently small monomer polarizabilities goes quite smoothly. On the contrary, when the monomer polarizability exceeds a certain threshold value, the globule-coil transition occurs as a dramatic expansion in the regime of first-order phase transition. The developed theoretical model can be applied to predicting polymer globule density change under external electric field in order to provide more efficient processes of polymer functionalization, such as sorption, dyeing, and chemical modification.

1,2-diketones promoted degradation of poly(epsilon-caprolactone)

NASA Astrophysics Data System (ADS)

Danko, Martin; Borska, Katarina; Ragab, Sherif Shaban; Janigova, Ivica; Mosnacek, Jaroslav

2012-07-01

Photochemical reactions of Benzil and Camphorquinone were used for modification of poly(ɛ-caprolactone) polymer films. Photochemistry of dopants was followed by infrared spectroscopy, changes on polymer chains of matrix were followed by gel permeation chromatography. Benzoyl peroxide was efficiently photochemically generated from benzyl in solid polymer matrix in the presence of air. Following decomposition of benzoyl peroxide led to degradation of matrix. Photochemical transformation of benzil in vacuum led to hydrogen abstraction from the polymer chains in higher extent, which resulted to chains recombination and formation of gel. Photochemical transformation of camphorquinone to corresponding camphoric peroxide was not observed. Only decrease of molecular weight of polymer matrix doped with camphorquinone was observed during the irradiation.

Self-Consistent Field Theories for the Role of Large Length-Scale Architecture in Polymers

NASA Astrophysics Data System (ADS)

Wu, David

At large length-scales, the architecture of polymers can be described by a coarse-grained specification of the distribution of branch points and monomer types within a molecule. This includes molecular topology (e.g., cyclic or branched) as well as distances between branch points or chain ends. Design of large length-scale molecular architecture is appealing because it offers a universal strategy, independent of monomer chemistry, to tune properties. Non-linear analogs of linear chains differ in molecular-scale properties, such as mobility, entanglements, and surface segregation in blends that are well-known to impact rheological, dynamical, thermodynamic and surface properties including adhesion and wetting. We have used Self-Consistent Field (SCF) theories to describe a number of phenomena associated with large length-scale polymer architecture. We have predicted the surface composition profiles of non-linear chains in blends with linear chains. These predictions are in good agreement with experimental results, including from neutron scattering, on a range of well-controlled branched (star, pom-pom and end-branched) and cyclic polymer architectures. Moreover, the theory allows explanation of the segregation and conformations of branched polymers in terms of effective surface potentials acting on the end and branch groups. However, for cyclic chains, which have no end or junction points, a qualitatively different topological mechanism based on conformational entropy drives cyclic chains to a surface, consistent with recent neutron reflectivity experiments. We have also used SCF theory to calculate intramolecular and intermolecular correlations for polymer chains in the bulk, dilute solution, and trapped at a liquid-liquid interface. Predictions of chain swelling in dilute star polymer solutions compare favorably with existing PRISM theory and swelling at an interface helps explain recent measurements of chain mobility at an oil-water interface. In collaboration with: Renfeng Hu, Colorado School of Mines, and Mark Foster, University of Akron. This work was supported by NSF Grants No. CBET- 0730692 and No. CBET-0731319.

Translocation of a Polymer Chain across a Nanopore: A Brownian Dynamics Simulation Study

NASA Technical Reports Server (NTRS)

Tian, Pu; Smith, Grant D.

2003-01-01

We carried out Brownian dynamics simulation studies of the translocation of single polymer chains across a nanosized pore under the driving of an applied field (chemical potential gradient). The translocation process can be either dominated by the entropic barrier resulted from restricted motion of flexible polymer chains or by applied forces (or chemical gradient across the wall), we focused on the latter case in our studies. Calculation of radius of gyrations at the two opposite sides of the wall shows that the polymer chains are not in equilibrium during the translocation process. Despite this fact, our results show that the one-dimensional diffusion and the nucleation model provide an excellent description of the dependence of average translocation time on the chemical potential gradients, the polymer chain length and the solvent viscosity. In good agreement with experimental results and theoretical predictions, the translocation time distribution of our simple model shows strong non-Gaussian characteristics. It is observed that even for this simple tubelike pore geometry, more than one peak of translocation time distribution can be generated for proper pore diameter and applied field strengths. Both repulsive Weeks-Chandler-Anderson and attractive Lennard-Jones polymer-nanopore interaction were studied, attraction facilitates the translocation process by shortening the total translocation time and dramatically improve the capturing of polymer chain. The width of the translocation time distribution was found to decrease with increasing temperature, increasing field strength, and decreasing pore diameter.

Method for polymer synthesis in a reaction well

DOEpatents

Brennan, Thomas M.

1998-01-01

A method of synthesis for building a polymer chain, oligonucleotides in particular, by sequentially adding monomer units to at least one solid support for growing and immobilizing a polymer chain thereon in a liquid reagent solution. The method includes the step of: A) depositing a liquid reagent in a reaction well (26) in contact with at least one solid support and at least one monomer unit of the polymer chain affixed to the solid support. The well (26) includes at least one orifice (74) extending into the well (26), and is of a size and dimension to form a capillary liquid seal to retain the reagent solution in the well (26) to enable polymer chain growth on the solid support. The method further includes the step of B) expelling the reagent solution from the well (26), while retaining the polymer chain therein. This is accomplished by applying a first gas pressure to the reaction well such that a pressure differential between the first gas pressure and a second gas pressure exerted on an exit (80) of the orifice (74) exceeds a predetermined amount sufficient to overcome the capillary liquid seal and expel the reagent solution from the well (26) through the orifice exit (80).

Method for polymer synthesis in a reaction well

DOEpatents

Brennan, T.M.

1998-09-29

A method of synthesis is described for building a polymer chain, oligonucleotides in particular, by sequentially adding monomer units to at least one solid support for growing and immobilizing a polymer chain thereon in a liquid reagent solution. The method includes the step of: (A) depositing a liquid reagent in a reaction well in contact with at least one solid support and at least one monomer unit of the polymer chain affixed to the solid support. The well includes at least one orifice extending into the well, and is of a size and dimension to form a capillary liquid seal to retain the reagent solution in the well to enable polymer chain growth on the solid support. The method further includes the step of (B) expelling the reagent solution from the well, while retaining the polymer chain therein. This is accomplished by applying a first gas pressure to the reaction well such that a pressure differential between the first gas pressure and a second gas pressure exerted on an exit of the orifice exceeds a predetermined amount sufficient to overcome the capillary liquid seal and expel the reagent solution from the well through the orifice exit. 9 figs.

Organization of polymer chains onto long, single-wall carbon nano-tubes: effect of tube diameter and cooling method.

PubMed

Kumar, Sunil; Pattanayek, Sudip K; Pereira, Gerald G

2014-01-14

We use molecular dynamics simulations to investigate the arrangement of polymer chains when absorbed onto a long, single-wall carbon nano-tube (SWCNT). We study the conformation and organization of the polymer chains on the SWCNT and their dependence on the tube's diameter and the rate of cooling. We use two types of cooling processes: direct quenching and gradual cooling. The radial density distribution function and bond orientational order parameter are used to characterize the polymer chain structure near the surface. In the direct cooling process, the beads of the polymer chain organize in lamella-like patterns on the surface of the SWCNT with the long axis of the lamella parallel to the axis of the SWCNT. In a stepwise, gradual cooling process, the polymer beads form a helical pattern on the surface of a relatively thick SWCNT, but form a lamella-like pattern on the surface of a very thin SWCNT. We develop a theoretical (free energy) model to explain this difference in pattern structures for the gradual cooling process and also provide a qualitative explanation for the pattern that forms from the direct cooling process.

Tailoring Thermal Conductivity of Single-stranded Carbon-chain Polymers through Atomic Mass Modification

PubMed Central

Liao, Quanwen; Zeng, Lingping; Liu, Zhichun; Liu, Wei

2016-01-01

Tailoring the thermal conductivity of polymers is central to enlarge their applications in the thermal management of flexible integrated circuits. Progress has been made over the past decade by fabricating materials with various nanostructures, but a clear relationship between various functional groups and thermal properties of polymers remains to be established. Here, we numerically study the thermal conductivity of single-stranded carbon-chain polymers with multiple substituents of hydrogen atoms through atomic mass modification. We find that their thermal conductivity can be tuned by atomic mass modifications as revealed through molecular dynamics simulations. The simulation results suggest that heavy homogeneous substituents do not assist heat transport and trace amounts of heavy substituents can in fact hinder heat transport substantially. Our analysis indicates that carbon chain has the biggest contribution (over 80%) to the thermal conduction in single-stranded carbon-chain polymers. We further demonstrate that atomic mass modifications influence the phonon bands of bonding carbon atoms, and the discrepancies of phonon bands between carbon atoms are responsible for the remarkable drops in thermal conductivity and large thermal resistances in carbon chains. Our study provides fundamental insight into how to tailor the thermal conductivity of polymers through variable substituents. PMID:27713563

Molecular Design of Antifouling Polymer Brushes Using Sequence-Specific Peptoids.

PubMed

Lau, King Hang Aaron; Sileika, Tadas S; Park, Sung Hyun; Sousa, Ana Maria Leal; Burch, Patrick; Szleifer, Igal; Messersmith, Phillip B

2015-01-07

Material systems that can be used to flexibly and precisely define the chemical nature and molecular arrangement of a surface would be invaluable for the control of complex biointerfacial interactions. For example, progress in antifouling polymer biointerfaces that prevent non-specific protein adsorption and cell attachment, which can significantly improve the performance of an array of biomedical and industrial applications, is hampered by a lack of chemical models to identify the molecular features conferring their properties. Poly(N-substituted glycine) "peptoids" are peptidomimetic polymers that can be conveniently synthesized with specific monomer sequences and chain lengths, and are presented as a versatile platform for investigating the molecular design of antifouling polymer brushes. Zwitterionic antifouling polymer brushes have captured significant recent attention, and a targeted library of zwitterionic peptoid brushes with a different charge densities, hydration, separations between charged groups, chain lengths, and grafted chain densities, is quantitatively evaluated for their antifouling properties through a range of protein adsorption and cell attachment assays. Specific zwitterionic brush designs were found to give rise to distinct but subtle differences in properties. The results also point to the dominant roles of the grafted chain density and chain length in determining the performance of antifouling polymer brushes.

Structure and Entanglement Factors on Dynamics of Polymer-Grafted Nanoparticles

DOE PAGES

Liu, Siqi; Senses, Erkan; Jiao, Yang; ...

2016-04-15

Nanoparticles functionalized with long polymer chains at low graft density are interesting systems to study structure–dynamic relationships in polymer nanocomposites since they are shown to aggregate into strings in both solution and melts and also into spheres and branched aggregates in the presence of free polymer chains. Our work investigates structure and entanglement effects in composites of polystyrene-grafted iron oxide nanoparticles by measuring particle relaxations using X-ray photon correlation spectroscopy. And for particles within highly ordered strings and aggregated systems, they experience a dynamically heterogeneous environment displaying hyperdiffusive relaxation commonly observed in jammed soft glassy systems. Furthermore, particle dynamics ismore » diffusive for branched aggregated structures which could be caused by less penetration of long matrix chains into brushes. These results suggest that particle motion is dictated by the strong interactions of chains grafted at low density with the host matrix polymer.« less

Molecular Strategies for Morphology Control in Semiconducting Polymers for Optoelectronics.

PubMed

Rahmanudin, Aiman; Sivula, Kevin

2017-06-28

Solution-processable semiconducting polymers have been explored over the last decades for their potential applications in inexpensively fabricated transistors, diodes and photovoltaic cells. However, a remaining challenge in the field is to control the solid-state self-assembly of polymer chains in thin films devices, as the aspects of (semi)crystallinity, grain boundaries, and chain entanglement can drastically affect intra-and inter-molecular charge transport/transfer and thus device performance. In this short review we examine how the aspects of molecular weight and chain rigidity affect solid-state self-assembly and highlight molecular engineering strategies to tune thin film morphology. Side chain engineering, flexibly linking conjugation segments, and block co-polymer strategies are specifically discussed with respect to their effect on field effect charge carrier mobility in transistors and power conversion efficiency in solar cells. Example systems are taken from recent literature including work from our laboratories to illustrate the potential of molecular engineering semiconducting polymers.

Synthesis, surface characterization, and biointeraction studies of low-surface energy side-chain polyetherurethanes

NASA Astrophysics Data System (ADS)

Porter, Stephen Christopher

1999-10-01

New segmented polyetherurethanes (PEUs) with low surface energy hydrocarbon and fluorocarbon side-chains attached to the polymer hard segments were synthesized. The surface chemistry of solvent cast polymer films was studied using X-ray photoelectron spectroscopy, time-of-flight secondary ion mass spectrometry, and dynamic contact angle (DCA) measurements. Increases in the overall density and length of the alkyl side-chains within the PEUs resulted in greater side-chain concentrations at the polymer surface. PEUs bearing long alkyl (> C10 ) and perfluorocarbon side-chains were found to posses surfaces with highly enriched side-chain concentrations relative to the bulk polymer. In PEUs with significant side-chain surface enrichment, the relatively polar hard segment blocks were shown to reside in high concentrations just below the side-chain enriched surface layer. Furthermore, DCA measurements demonstrated that the surface of the alkyl side-chain PEUs did not undergo significant rearrangement when placed into an aqueous environment, whereas the surface of a hard segment model polymer bearing C18 sidechains (PEU-C18-HS) did. Hydrogen bonding within the PEUs was examined using FTIR and was shown to be disrupted by the addition of side-chains; an effect dependent on the density but not on the length of the side-chains. Heteropolymer blends comprised of mixtures of high side-chain density and side-chain free PEUs were compared with homopolymers having the same overall side-chain concentration as the blends. Significantly more surface enrichment of side-chains was found in the heteropolymer blends whereas hydrogen bonding nearly the same as in the homopolymers. Adsorption of native and delipidized human serum albumin (HSA) from pure solution and blood plasma; the elutabilty of adsorbed HSA; and static platelet adhesion to plasma preadsorbed surfaces, were all examined on alkyl side-chain PEUs. Several polymers with high C18 side-chain densities displayed increased affinity for albumin, and reduced elutability. Among these, PEU-C18-HS demonstrated a significant reduction in platelet adhesion at low plasma pre-adsorption concentrations. However, competitive binary adsorption of fibrinogen in the presence of HSA demonstrated lower relative albumin affinity for PEU-C18-HS than other PEUs. The observed effects are thought to be mainly a result of increased surface hydrophobicity of the alkyl-side chain modified PEU, and not high specificity albumin binding.

Initiation and strain compatibility of connected extension twins in AZ31 magnesium alloy at high temperature

DOE Office of Scientific and Technical Information (OSTI.GOV)

Liu, Xiao, E-mail: liuxiao0105@163.com

2016-12-15

Uniaxial compression tests were carried out at 350 °C and a strain rate of 0.3 s{sup −1} on as-extruded AZ31 magnesium alloy samples. At a true strain of − 0.1, extension twin pairs in a grain and twin chains across adjacent grains were detected. The orientation of selected twins and their host grains were determined by electron backscattered diffraction (EBSD) techniques. The Schmid factors (SFs), accommodation strains and geometric compatibility factors (m{sup ′}) were calculated. Analysis of the data indicated that the formation of twin pair and twin chain was related to the SF and m{sup ′}. Regarding to twinmore » chain across adjacent grains, accommodation strain was also involved. The selection of twin variants in twin chain was generally determined by m{sup ′}. When the twins required the operation of pyramidal slip or twinning in adjacent grain, the corresponding connected twins with a relative high m{sup ′} were selected in this adjacent grain. - Highlights: •The formation of paired twins is studied during high temperature deformation. •The initiation of twinning in twin pair and twin chain obeys the Schmid law. •The twin variants' selection in twin chain is related to the geometric compatibility factor. •The accommodation strain plays an important role on the formation of twin chain.« less

Relaxation and Self-Diffusion of a Polymer Chain in a Melt

NASA Astrophysics Data System (ADS)

Hagita, Katsumi; Takano, Hiroshi

2004-04-01

Relaxation and self-diffusion of a polymer chain in a melt are discussed on the basis of the results of our recent Monte Carlo simulations of the bond fluctuation model, where only the excluded volume interaction is considered. Polymer chains are located on an L × L × L simple cubic lattice under periodic boundary conditions. Each chain consists of N segments, each of which occupies 2 × 2 × 2 unit cells. The results for N = 32, 48, 64, 96, 128, 192, 256, 384 and 512 at the volume fraction φ ≃ 0.5 are examined, where L = 128 for N ⩽ 256 and L = 192 for N ⩾ 384. The longest relaxation time τ is estimated by solving generalized eigenvalue problems for the equilibrium time correlation matrices of the positions of segments of a polymer chain. The self-diffusion constant D is estimated from the mean square displacements of the center of mass of a single polymer chain at the times larger than τ. From the data for N = 256, 384 and 512, the apparent exponents x r and xd, which describe the power law dependences of τ and D on N as τ ∝ N xr and D ∝ N-xd, are estimated to be xr ≃ 3.5 and xd ≃ 2.4, respectively. For N = 192, 256, 384 and 512, Dτ/ appears to be a constant, where denotes the mean square end-to-end distance of a polymer chain.

Polymer Brush Grafted Nanoparticles and Their Impact on the Morphology Evolution of Polymer Blend Films

NASA Astrophysics Data System (ADS)

Chung, Hyun-Joong; Ohno, Kohji; Composto, Russell

2013-03-01

We present an novel pathway to control the location of nanoparticles (NPs) in phase-separating polymer blend films containing poly(methyl methacrylate) (PMMA) and poly(styrene-ran-acrylonitrile) (SAN). Because hydrophobic polymer phases have a small interfacial energy, ~1 mJ/m2, subtle changes in the NP surface functionality can be used to guide NPs to either the interface between immiscible polymers or into one of the phases. Based on this idea, we designed a class of NPs grafted with PMMA brushes. These PMMA brushes were grown from the NP surface by atom transfer radical polymerization (ATRP), which results in chains terminated with chlorine atoms. The chain end can be substituted with protons (H) by dehalogenation. As a result, the NPs are strongly segregated at the interface when grafted PMMA chains are short (Mn =1.8K) and the end group is Cl, whereas NPs partition into PMMA-rich phase when chains are long (Mn =160K) and/or when chains are terminated with hydrogen. The Cl end groups and shorter chain length cause an increase in surface energy for the NPs. The increase in surface energy of short-chained NPs can be attributed to (i) an extended brush conformation (entropic) and/or (ii) a high density of ``unfavorable'' end groups (enthalpic). Finally, the impact of NPs on the morphological evolution of the polymer blend films will be discussed. Ref: H.-J.Chung et al., ACS Macro Lett. 1(1), 252-256 (2012).

Thermoresponsive AuNPs Stabilized by Pillararene-Containing Polymers.

PubMed

Liao, Xiaojuan; Guo, Lei; Chang, Junxia; Liu, Sha; Xie, Meiran; Chen, Guosong

2015-08-01

Pillararene-containing thermoresponsive polymers are synthesized via reversible addition-fragmentation chain transfer polymerization using pillararene derivatives as the effective chain transfer agents for the first time. These polymers can self-assemble into micelles and form vesicles after guest molecules are added. Furthermore, such functional polymers can be further applied to prepare hybrid gold nanoparticles, which integrate the thermoresponsivity of polymers and molecular recognition of pillararenes. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Polymer dynamics in turbulent flow

NASA Astrophysics Data System (ADS)

Muthukumar, Murugappan

2014-03-01

Presence of dilute amounts of high-molecular weight polymers in liquids undergoing turbulent wall-bounded shear flows leads to significant drag reduction. There are two major proposed mechanisms of drag reduction in the literature. One is based on enhanced viscosity due to chain extension; the other is based on the assumption that elastic energy stored in polymer conformations is comparable to the kinetic energy in some eddies. Using the Navier-Stokes equation for the fluid and the Kirkwood-Riseman-Zimm equation for polymer chains, we have addressed the coupling between the near-wall turbulence dynamics and polymer dynamics. Our theoretical results show that the torque associated with polymer conformations contributes more significantly than the chain stretching and that the characteristic dimensions of polymer coils are much smaller than eddy sizes required for possible exchange of energy. We thus emphasize an additional mechanism to the existing two schools of thought in the search of an understanding of drag reduction.

Self assembled linear polymeric chains with tuneable semiflexibility using isotropic interactions.

PubMed

Abraham, Alex; Chatterji, Apratim

2018-04-21

We propose a two-body spherically symmetric (isotropic) potential such that particles interacting by the potential self-assemble into linear semiflexible polymeric chains without branching. By suitable control of the potential parameters, we can control the persistence length of the polymer and can even introduce a controlled number of branches. Thus we show how to achieve effective directional interactions starting from spherically symmetric potentials. The self-assembled polymers have an exponential distribution of chain lengths akin to what is observed for worm-like micellar systems. On increasing particle density, the polymeric chains self-organize to an ordered line-hexagonal phase where every chain is surrounded by six parallel chains, the transition is first order. On further increase in monomer density, the order is destroyed and we get a branched gel-like phase. This potential can be used to model semi-flexible equilibrium polymers with tunable semiflexibility and excluded volume. The use of the potential is computationally cheap and hence can be used to simulate and probe equilibrium polymer dynamics with long chains. The potential also gives a plausible method of tuning colloidal interactions in experiments such that one can obtain self-assembling polymeric chains made up of colloids and probe polymer dynamics using an optical microscope. Furthermore, we show how a modified potential leads to the observation of an intermediate nematic phase of self-assembled chains in between the low density disordered phase and the line-ordered hexagonal phase.

Self assembled linear polymeric chains with tuneable semiflexibility using isotropic interactions

NASA Astrophysics Data System (ADS)

Abraham, Alex; Chatterji, Apratim

2018-04-01

We propose a two-body spherically symmetric (isotropic) potential such that particles interacting by the potential self-assemble into linear semiflexible polymeric chains without branching. By suitable control of the potential parameters, we can control the persistence length of the polymer and can even introduce a controlled number of branches. Thus we show how to achieve effective directional interactions starting from spherically symmetric potentials. The self-assembled polymers have an exponential distribution of chain lengths akin to what is observed for worm-like micellar systems. On increasing particle density, the polymeric chains self-organize to an ordered line-hexagonal phase where every chain is surrounded by six parallel chains, the transition is first order. On further increase in monomer density, the order is destroyed and we get a branched gel-like phase. This potential can be used to model semi-flexible equilibrium polymers with tunable semiflexibility and excluded volume. The use of the potential is computationally cheap and hence can be used to simulate and probe equilibrium polymer dynamics with long chains. The potential also gives a plausible method of tuning colloidal interactions in experiments such that one can obtain self-assembling polymeric chains made up of colloids and probe polymer dynamics using an optical microscope. Furthermore, we show how a modified potential leads to the observation of an intermediate nematic phase of self-assembled chains in between the low density disordered phase and the line-ordered hexagonal phase.

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

PubMed

Voortman, Thomas P; Chiechi, Ryan C

2015-12-30

This paper compares the morphologies of films of conjugated polymers in which the backbone (main chain) and pendant groups are varied between ionic/hydrophilic and aliphatic/hydrophobic. We observe that conjugated polymers in which the pendant groups and backbone are matched, either ionic-ionic or hydrophobic-hydrophobic, form smooth, structured, homogeneous films from water (ionic) or tetrahydrofuran (hydrophobic). Mismatched conjugated polymers, by contrast, form inhomogeneous films with rough topologies. The polymers with ionic backbone chains are conjugated polyions (conjugated polymers with closed-shell charges in the backbone), which are semiconducting materials with tunable bad-gaps, not unlike uncharged conjugated polymers.

Surface functionalization of quantum dots with fine-structured pH-sensitive phospholipid polymer chains.

PubMed

Liu, Yihua; Inoue, Yuuki; Ishihara, Kazuhiko

2015-11-01

To add novel functionality to quantum dots (QDs), we synthesized water-soluble and pH-responsive block-type polymers by reversible addition-fragmentation chain transfer (RAFT) polymerization. The polymers were composed of cytocompatible 2-methacryloyloxyethyl phosphorylcholine (MPC) polymer segments, which contain a small fraction of active ester groups and can be used to conjugate biologically active compounds to the polymer, and pH-responsive poly(2-(N,N-diethylamino) ethyl methacrylate (DEAEMA)) segments. One terminal of the polymer chain had a hydrophobic alkyl group that originated from the RAFT initiator. This hydrophobic group can bind to the hydrophobic layer on the QD surface. A fluorescent dye was conjugated to the polymer chains via the active ester group. The block-type polymers have an amphiphilic nature in aqueous medium. The polymers were thus easily bound to the QD surface upon evaporation of the solvent from a solution containing the block-type polymer and QDs, yielding QD/fluorescence dye-conjugated polymer hybrid nanoparticles. Fluorescence resonance energy transfer (FRET) between the QDs (donors) and the fluorescent dye molecules (acceptors) was used to obtain information on the conformational dynamics of the immobilized polymers. Higher FRET efficiency of the QD/fluorescent dye-conjugated polymer hybrid nanoparticles was observed at pH 7.4 as compared to pH 5.0 due to a stretching-shrinking conformational motion of the poly(DEAEMA) segments in response to changes in pH. We concluded that the block-type MPC polymer-modified nanoparticles could be used to evaluate the pH of cells via FRET fluorescence based on the cytocompatibility of the MPC polymer. Copyright © 2015 Elsevier B.V. All rights reserved.

Side chain engineering of poly-thiophene and its impact on crystalline silicon based hybrid solar cells

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zellmeier, M.; Rappich, J.; Nickel, N. H.

The influence of ether groups in the side chain of spin coated regioregular polythiophene derivatives on the polymer layer formation and the hybrid solar cell properties was investigated using electrical, optical, and X-ray diffraction experiments. The polymer layers are of high crystallinity but the polymer with 3 ether groups in the side chain (P3TOT) did not show any vibrational fine structure in the UV-Vis spectrum. The presence of ether groups in the side chains leads to better adhesion resulting in thinner and more homogeneous polymer layers. This, in turn, enhances the electronic properties of the planar c-Si/poly-thiophene hybrid solar cell.more » We find that the power conversion efficiency increases with the number of ether groups in the side chains, and a maximum power conversion efficiency of η = 9.6% is achieved even in simple planar structures.« less

Diketopyrrolopyrrole-Based Conjugated Polymer Entailing Triethylene Glycols as Side Chains with High Thin-Film Charge Mobility without Post-Treatments

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yang, Si-Fen; Liu, Zi-Tong; Cai, Zheng-Xu

Side chain engineering of conjugated donor-acceptor polymers is a new way to manipulate their optoelectronic properties. Two new diketopyrrolopyrrole (DPP)-terthiophene-based conjugated polymers PDPP3T-1 and PDPP3T-2, with both hydrophilic triethylene glycol (TEG) and hydrophobic alkyl chains, are reported. It is demonstrated that the incorporation of TEG chains has a significant effect on the interchain packing and thin-film morphology with noticeable effect on charge transport. Polymer chains of PDPP3T-1 in which TEG chains are uniformly distributed can self-assemble spontaneously into a more ordered thin film. As a result, the thin film of PDPP3T-1 exhibits high saturated hole mobility up to 2.6 cm(2)more » V-1 s(-1) without any post-treatment. This is superior to those of PDPP3T with just alkyl chains and PDPP3T-2. Moreover, the respective field effect transistors made of PDPP3T-1 can be utilized for sensing ethanol vapor with high sensitivity (down to 100 ppb) and good selectivity.« less

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.

Liquid Crystalline Polymers Containing Heterocycloalkane Mesogens. 1. Side-Chain Liquid Crystalline Polymethacrylates and Polycrylates Containing 2,5-Disubstituted-1,3-Dioxane Mesogens.

DTIC Science & Technology

1986-10-01

Report No. 2 Liquid Crystalline Polymers Containing Heterocycloalkane Mesogeus 1. Side-Chain Liquid Crystalline Polymethacrylates and . Polyacrylates...8217. " "-"-"-" " "" ’CS" i Liquid Crystalline Polymers Containing Heterocycloalkane Mesogens 1. Side-Chain Liquid Crystalline Polymethacrylates and Polyacrylates...University Cleveland, OH 44106 ABSTRACT Polymethacrylates and polyacrylates containing 2-(p-hydroxyphenyl)-5-(p-meth- oxyphenyl)-1,3-dioxane as a

Single chain technology: Toward the controlled synthesis of polymer nanostructures

NASA Astrophysics Data System (ADS)

Lyon, Christopher

A technique for fabricating advanced polymer nanostructures enjoying recent popularity is the collapse or folding of single polymer chains in highly dilute solution mediated by intramolecular cross-linking. We term the resultant structures single-chain nanoparticles (SCNP). This technique has proven particularly valuable in the synthesis of nanomaterials on the order of 5 -- 20 nm. Many different types of covalent and non-covalent chemistries have been used to this end. This dissertation investigates the use of so-called single-chain technology to synthesize nanoparticles using modular techniques that allow for easy incorporation of functionality or special structural or characteristic features. Specifically, the synthesis of linear polymers functionalized with pendant monomer units and the subsequent intramolecular polymerization of these monomer units is discussed. In chapter 2, the synthesis of SCNP using alternating radical polymerization is described. Polymers functionalized with pendant styrene and stilbene groups are synthesized via a modular post-polymerization Wittig reaction. These polymers were exposed to radical initiators in the presence (and absence) of maleic anhydride and other electron deficient monomers in order to form intramolecular cross-links. Chapter 3 discusses templated acyclic diene metathesis (ADMET) polymerization using single-chain technology, starting with the controlled ring-opening polymerization of a glycidyl ether functionalized with an ADMET monomer. This polymer was then exposed to Grubbs' catalyst to polymerize the ADMET monomer units. The ADMET polymer was hydrolytically cleaved from the template and separated. Upon characterization, it was found that the daughter ADMET polymer had a similar degree of polymerization, but did not retain the low dispersity of the template. Chapter 4 details the synthesis of aldehyde- and diol-functionalized polymers toward the synthesis of SCNP containing dynamic, acid-degradable acetal cross-links. SCNP fabrication with these materials is beyond the scope of this dissertation.

Creep-induced anisotropy in covalent adaptable network polymers.

PubMed

Hanzon, Drew W; He, Xu; Yang, Hua; Shi, Qian; Yu, Kai

2017-10-11

Anisotropic polymers with aligned macromolecule chains exhibit directional strengthening of mechanical and physical properties. However, manipulating the orientation of polymer chains in a fully cured thermoset is almost impossible due to its permanently crosslinked nature. In this paper, we demonstrate that rearrangeable networks with bond exchange reactions (BERs) can be utilized to tailor the anisotropic mechanical properties of thermosetting polymers. When a constant force is maintained at BER activated temperatures, the malleable thermoset creeps in the direction of stress, and macromolecule chains align themselves in the same direction. The aligned polymer chains result in an anisotropic network with a stiffer mechanical behavior in the direction of creep, while with a more compliant behavior in the transverse direction. The degree of network anisotropy is proportional to the amount of creep strain. A multi-length scale constitutive model is developed to study the creep-induced anisotropy of thermosetting polymers. The model connects the micro-scale BER kinetics, orientation of polymer chains, and directional mechanical properties of network polymers. Without any fitting parameters, it is able to predict the evolution of creep strain at different temperatures and anisotropic stress-strain behaviors of CANs after creep. Predictions on the chain orientation are verified by molecular dynamics (MD) simulation. Based on parametric studies, it is shown that the influences of creep time and temperature on the network anisotropy can be generalized into a single parameter, and the evolution of directional modulus follows an Arrhenius type time-temperature superposition principle (TTSP). The presented work provides a facile approach to transform isotropic thermosets into anisotropic ones using simple heating, and their directional properties can be readily tailored by the processing conditions.

Poly(glycidyl ether)-Based Monolayers on Gold Surfaces: Control of Grafting Density and Chain Conformation by Grafting Procedure, Surface Anchor, and Molecular Weight.

PubMed

Heinen, Silke; Weinhart, Marie

2017-03-07

For a meaningful correlation of surface coatings with their respective biological response reproducible coating procedures, well-defined surface coatings, and thorough surface characterization with respect to layer thickness and grafting density are indispensable. The same applies to polymeric monolayer coatings which are intended to be used for, e.g., fundamental studies on the volume phase transition of surface end-tethered thermoresponsive polymer chains. Planar gold surfaces are frequently used as model substrates, since they allow a variety of straightforward surface characterization methods. Herein we present reproducible grafting-to procedures performed with thermoresponsive poly(glycidyl ether) copolymers composed of glycidyl methyl ether (GME) and ethyl glycidyl ether (EGE). The copolymers feature different molecular weights (2 kDa, 9 kDa, 24 kDa) and are equipped with varying sulfur-containing anchor groups in order to achieve adjustable grafting densities on gold surfaces and hence control the tethered polymers' chain conformation. We determined "wet" and "dry" thicknesses of these coatings by QCM-D and ellipsometry measurements and deduced anchor distances and degrees of chain overlap of the polymer chains assembled on gold. Grafting under cloud point conditions allowed for higher degrees of chain overlap compared to grafting from a good solvent like ethanol, independent of the used sulfur-containing anchor group for polymers with low (2 kDa) and medium (9 kDa) molecular weights. By contrast, the achieved grafting densities and thus chain overlaps of surface-tethered polymers with high (24 kDa) molecular weights were identical for both grafting methods. Monolayers prepared from an ethanolic solution of poly(glycidyl ether)s equipped with sterically demanding disulfide-containing anchors revealed the lowest degrees of chain overlap. The ratio of the radius of gyration to the anchor distance (2 R g /l) of the latter coating was found to be lower than 1.4, indicating that the assembly was rather in the mushroom-like than in the brush regime. Polymer chains with thiol-containing anchors of different alkyl chain lengths (C 11 SH vs C 4 SH) formed assemblies with comparable degrees of chain overlap with 2 R g /l values above 1.4 and are thus in the brush regime. Molecular weights influenced the achievable degree of chain overlap on the surface. Coatings prepared with the medium molecular weight polymer (9 kDa) resulted in the highest chain packing density. Control of grafting density and thus chain overlap in different regimes (brush vs mushroom) on planar gold substrates are attainable for monolayer coatings with poly(GME-ran-EGE) by adjusting the polymer's molecular weight and anchor group as well as the conditions for the grafting-to procedure.

1,2-diketones promoted degradation of poly(epsilon-caprolactone)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Danko, Martin; Borska, Katarina; Ragab, Sherif Shaban

2012-07-11

Photochemical reactions of Benzil and Camphorquinone were used for modification of poly({epsilon}-caprolactone) polymer films. Photochemistry of dopants was followed by infrared spectroscopy, changes on polymer chains of matrix were followed by gel permeation chromatography. Benzoyl peroxide was efficiently photochemically generated from benzyl in solid polymer matrix in the presence of air. Following decomposition of benzoyl peroxide led to degradation of matrix. Photochemical transformation of benzil in vacuum led to hydrogen abstraction from the polymer chains in higher extent, which resulted to chains recombination and formation of gel. Photochemical transformation of camphorquinone to corresponding camphoric peroxide was not observed. Only decreasemore » of molecular weight of polymer matrix doped with camphorquinone was observed during the irradiation.« less

End-functionalized ROMP polymers for Biomedical Applications

PubMed Central

Madkour, Ahmad E.; Koch, Amelie H. R.; Lienkamp, Karen; Tew, Gregory N.

2010-01-01

We present two novel allyl-based terminating agents that can be used to end-functionalize living polymer chains obtained by ring-opening metathesis polymerization (ROMP) using Grubbs’ third generation catalyst. Both terminating agents can be easily synthesized and yield ROMP polymers with stable, storable activated ester groups at the chain-end. These end-functionalized ROMP polymers are attractive building blocks for advanced polymeric materials, especially in the biomedical field. Dye-labeling and surface-coupling of antimicrobially active polymers using these end-groups were demonstrated. PMID:21499549

Compression induced phase transition of nematic brush: A mean-field theory study

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tang, Jiuzhou; Zhang, Xinghua, E-mail: zhangxh@bjtu.edu.cn; Yan, Dadong, E-mail: yandd@bnu.edu.cn

2015-11-28

Responsive behavior of polymer brush to the external compression is one of the most important characters for its application. For the flexible polymer brush, in the case of low grafting density, which is widely studied by the Gaussian chain model based theory, the compression leads to a uniform deformation of the chain. However, in the case of high grafting density, the brush becomes anisotropic and the nematic phase will be formed. The normal compression tends to destroy the nematic order, which leads to a complex responsive behaviors. Under weak compression, chains in the nematic brush are buckled, and the bendingmore » energy and Onsager interaction give rise to the elasticity. Under deep compression, the responsive behaviors of the nematic polymer brush depend on the chain rigidity. For the compressed rigid polymer brush, the chains incline to re-orientate randomly to maximize the orientational entropy and its nematic order is destroyed. For the compressed flexible polymer brush, the chains incline to fold back to keep the nematic order. A buckling-folding transition takes place during the compressing process. For the compressed semiflexible brush, the chains are collectively tilted to a certain direction, which leads to the breaking of the rotational symmetry in the lateral plane. These responsive behaviors of nematic brush relate to the properties of highly frustrated worm-like chain, which is hard to be studied by the traditional self-consistent field theory due to the difficulty to solve the modified diffusion equation. To overcome this difficulty, a single chain in mean-field theory incorporating Monte Carlo simulation and mean-field theory for the worm-like chain model is developed in present work. This method shows high performance for entire region of chain rigidity in the confined condition.« less

[Using Molecular Simulations to Understand Complex Nanoscale Dynamic Phenomena in Polymer Solutions

NASA Technical Reports Server (NTRS)

Smith, Grant

2004-01-01

The first half of the project concentrated on molecular simulation studies of the translocation of model molecules for single-stranded DNA through a nanosized pore. This has resulted in the publication, Translocation of a polymer chain across a nanopore: A Brownian dynamics simulation study, by Pu Tian and Grant D. Smith, JOURNAL OF CHEMICAL PHYSICS VOLUME 119, NUMBER 21 1 DECEMBER 2003, which is attached to this report. In this work we carried out Brownian dynamics simulation studies of the translocation of single polymer chains across a nanosized pore under the driving of an applied field (chemical potential gradient) designed to mimic an electrostatic field. The translocation process can be either dominated by the entropic barrier resulted from restricted motion of flexible polymer chains or by applied forces (or chemical gradient). We focused on the latter case in our studies. Calculation of radius of gyration of the translocating chain at the two opposite sides of the wall shows that the polymer chains are not in equilibrium during the translocation process. Despite this fact, our results show that the one-dimensional diffusion and the nucleation model provide an excellent description of the dependence of average translocation time on the chemical potential gradients, the polymer chain length and the solvent viscosity. In good agreement with experimental results and theoretical predictions, the translocation time distribution of our simple model shows strong non-Gaussian characteristics. It is observed that even for this simple tube-like pore geometry, more than one peak of translocation time distribution can be generated for proper pore diameter and applied field strengths. Both repulsive Weeks-Chandler-Anderson and attractive Lennard-Jones polymer-nanopore interaction were studied. Attraction facilitates the translocation process by shortening the total translocation time and dramatically improve the capturing of polymer chain. The width of the translocation time distribution was found to decrease with increasing temperature, increasing field strength, and decreasing pore diameter.

Topological ferrimagnetic behaviours of coordination polymers containing manganese(II) chains with mixed azide and carboxylate bridges and alternating F/AF/AF'/AF'/AF interactions.

PubMed

Wang, Yan-Qin; Liu, Hou-Ting; Qi, Yan; Gao, En-Qing

2014-08-21

Two Mn(ii) complexes with azide and a new zwitterionic tetracarboxylate ligand 1,2,4,5-tetrakis(4-carboxylatopyridinium-1-methylene)benzene (L(1)), {[Mn5(L(1))2(N3)8(OH)2]·12H2O}n () and {[Mn5(L(1))2(N3)8(H2O)2](ClO4)2·6H2O}n (), have been synthesized and characterized crystallographically and magnetically. and contain similar alternating chains constructed by azide and carboxylate bridges. The independent sets of bridges alternate in an ABCCB sequence between adjacent Mn(ii) ions: (EO-N3)2 double bridges (EO = end-on) (denoted as A), [(EO-N3)(OCO)2] triple bridges (denoted as B) and [(EO-N3)(OCO)] double bridges (denoted as C). The alternating chains are interlinked into 2D coordination networks by the tetrapyridinium spacers. Magnetic studies demonstrate that the magnetic coupling through the double EO azide bridges is ferromagnetic and that through mixed azide/carboxylate bridges is antiferromagnetic. The unprecedented F/AF/AF'/AF'/AF coupling sequence along the chain dictates an uncompensated ground spin state (S = 5/2 per Mn5 unit) and leads to one-dimensional topological ferrimagnetism, which features a minimum in the χT versus T plot.

Electrophoretic mobilities of counterions and a polymer in cylindrical pores

PubMed Central

Singh, Sunil P.; Muthukumar, M.

2014-01-01

We have simulated the transport properties of a uniformly charged flexible polymer chain and its counterions confined inside cylindrical nanopores under an external electric field. The hydrodynamic interaction is treated by describing the solvent molecules explicitly with the multiparticle collision dynamics method. The chain consisting of charged monomers and the counterions interact electrostatically with themselves and with the external electric field. We find rich behavior of the counterions around the polymer under confinement in the presence of the external electric field. The mobility of the counterions is heterogeneous depending on their location relative to the polymer. The adsorption isotherm of the counterions on the polymer depends nonlinearly on the electric field. As a result, the effective charge of the polymer exhibits a sigmoidal dependence on the electric field. This in turn leads to a nascent nonlinearity in the chain stretching and electrophoretic mobility of the polymer in terms of their dependence on the electric field. The product of the electric field and the effective polymer charge is found to be the key variable to unify our simulation data for various polymer lengths. Chain extension and the electrophoretic mobility show sigmoidal dependence on the electric field, with crossovers from the linear response regime to the nonlinear regime and then to the saturation regime. The mobility of adsorbed counterions is nonmonotonic with the electric field. For weaker and moderate fields, the adsorbed counterions move with the polymer and at higher fields they move opposite to the polymer's direction. We find that the effective charge and the mobility of the polymer decrease with a decrease in the pore radius. PMID:25240366

Covalent bond force profile and cleavage in a single polymer chain

NASA Astrophysics Data System (ADS)

Garnier, Lionel; Gauthier-Manuel, Bernard; van der Vegte, Eric W.; Snijders, Jaap; Hadziioannou, Georges

2000-08-01

We present here the measurement of the single-polymer entropic elasticity and the single covalent bond force profile, probed with two types of atomic force microscopes (AFM) on a synthetic polymer molecule: polymethacrylic acid in water. The conventional AFM allowed us to distinguish two types of interactions present in this system when doing force spectroscopic measurements: the first interaction is associated with adsorption sites of the polymer chains onto a bare gold surface, the second interaction is directly correlated to the rupture process of a single covalent bond. All these bridging interactions allowed us to stretch the single polymer chain and to determine the various factors playing a role in the elasticity of these molecules. To obtain a closer insight into the bond rupture process, we moved to a force sensor stable in position when measuring attractive forces. By optimizing the polymer length so as to fulfill the elastic stability conditions, we were able for the first time to map out the entire force profile associated with the cleavage of a single covalent bond. Experimental data coupled with molecular quantum mechanical calculations strongly suggest that the breaking bond is located at one end of the polymer chain.

Dynamics in Polymer Nanocomposites

NASA Astrophysics Data System (ADS)

Clarke, Nigel

2015-03-01

Since nanoparticles are increasingly being added to polymers to impart mechanical and functional properties, we are exploring how nanoparticles impact polymer dynamics with a focus on the diffusion coefficients. In high molecular weight polymer melts, chain diffusion is well described by the reptation model. Motion proceeds as a snake-like diffusion of the chain as a whole, along the contour of a tube that mimics the role of physical entanglements, or topological constraints, with other chains. In polymer nanocomposites there are additional constraints due to the dispersed nanoparticles in the polymer matrix. Chain motion can be altered by nanoparticle size, shape , aspect ratio, surface area, loading and the nature of the interactions between the nanoparticles and the polymer matrix. We have observed a minimum in the diffusion coefficient as a function of nanoparticle concentration when the nanoparticles are rod-like and a collapse of the diffusion coefficient onto a master curve when the nanoparticles are spherical. We are simulating the dynamics using molecular and dissipative particle simulations in order to provide physical insight into the local structure and dynamics, and have also carried out highly coarse grained Monte Carlo simulations of entangled polymers to explore how reptation is affected by the presence of larger scale obstacles. We acknowledge support from the NSF/EPSRC Materials World Network Program.

Effect of bidispersity in grafted chain length on grafted chain conformations and potential of mean force between polymer grafted nanoparticles in a homopolymer matrix.

PubMed

Nair, Nitish; Wentzel, Nathaniel; Jayaraman, Arthi

2011-05-21

In efforts to produce polymeric materials with tailored physical properties, significant interest has grown around the ability to control the spatial organization of nanoparticles in polymer nanocomposites. One way to achieve controlled particle arrangement is by grafting the nanoparticle surface with polymers that are compatible with the matrix, thus manipulating the interfacial interactions between the nanoparticles and the polymer matrix. Previous work has shown that the molecular weight of the grafted polymer, both at high grafting density and low grafting density, plays a key role in dictating the effective inter-particle interactions in a polymer matrix. At high grafting density nanoparticles disperse (aggregate) if the graft molecular weight is higher (lower) than the matrix molecular weight. At low grafting density the longer grafts can better shield the nanoparticle surface from direct particle-particle contacts than the shorter grafts and lead to the dispersion of the grafted particles in the matrix. Despite the importance of graft molecular weight, and evidence of non-trivial effects of polydispersity of chains grafted on flat surfaces, most theoretical work on polymer grafted nanoparticles has only focused on monodisperse grafted chains. In this paper, we focus on how bidispersity in grafted chain lengths affects the grafted chain conformations and inter-particle interactions in an implicit solvent and in a dense homopolymer polymer matrix. We first present the effects of bidispersity on grafted chain conformations in a single polymer grafted particle using purely Monte Carlo (MC) simulations. This is followed by calculations of the potential of mean force (PMF) between two grafted particles in a polymer matrix using a self-consistent Polymer Reference Interaction Site Model theory-Monte Carlo simulation approach. Monte Carlo simulations of a single polymer grafted particle in an implicit solvent show that in the bidisperse polymer grafted particles with an equal number of short and long grafts at low to medium grafting density, the short grafts are in a more coiled up conformation (lower radius of gyration) than their monodisperse counterparts to provide a larger free volume to the longer grafts so they can gain conformational entropy. The longer grafts do not show much difference in conformation from their monodisperse counterparts at low grafting density, but at medium grafting density the longer grafts exhibit less stretched conformations (lower radius of gyration) as compared to their monodisperse counterparts. In the presence of an explicit homopolymer matrix, the longer grafts are more compressed by the matrix homopolymer chains than the short grafts. We observe that the potential of mean force between bidisperse grafted particles has features of the PMF of monodisperse grafted particles with short grafts and monodisperse grafted particles with long grafts. The value of the PMF at contact is governed by the short grafts and values at large inter-particle distances are governed by the longer grafts. Further comparison of the PMF for bidisperse and monodisperse polymer grafted particles in a homopolymer matrix at varying parameters shows that the effects of matrix chain length, matrix packing fraction, grafting density, and particle curvature on the PMF between bidisperse polymer grafted particles are similar to those seen between monodisperse polymer grafted particles. © 2011 American Institute of Physics.

Computational study of chain transfer to monomer reactions in high-temperature polymerization of alkyl acrylates.

PubMed

Moghadam, Nazanin; Liu, Shi; Srinivasan, Sriraj; Grady, Michael C; Soroush, Masoud; Rappe, Andrew M

2013-03-28

This article presents a computational study of chain transfer to monomer (CTM) reactions in self-initiated high-temperature homopolymerization of alkyl acrylates (methyl, ethyl, and n-butyl acrylate). Several mechanisms of CTM are studied. The effects of the length of live polymer chains and the type of monoradical that initiated the live polymer chains on the energy barriers and rate constants of the involved reaction steps are investigated theoretically. All calculations are carried out using density functional theory. Three types of hybrid functionals (B3LYP, X3LYP, and M06-2X) and four basis sets (6-31G(d), 6-31G(d,p), 6-311G(d), and 6-311G(d,p)) are applied to predict the molecular geometries of the reactants, products and transition sates, and energy barriers. Transition state theory is used to estimate rate constants. The results indicate that abstraction of a hydrogen atom (by live polymer chains) from the methyl group in methyl acrylate, the methylene group in ethyl acrylate, and methylene groups in n-butyl acrylate are the most likely mechanisms of CTM. Also, the rate constants of CTM reactions calculated using M06-2X are in good agreement with those estimated from polymer sample measurements using macroscopic mechanistic models. The rate constant values do not change significantly with the length of live polymer chains. Abstraction of a hydrogen atom by a tertiary radical has a higher energy barrier than abstraction by a secondary radical, which agrees with experimental findings. The calculated and experimental NMR spectra of dead polymer chains produced by CTM reactions are comparable. This theoretical/computational study reveals that CTM occurs most likely via hydrogen abstraction by live polymer chains from the methyl group of methyl acrylate and methylene group(s) of ethyl (n-butyl) acrylate.

Nanoparticle stability in semidilute and concentrated polymer solutions.

PubMed

Dutta, Nupur; Green, David

2008-05-20

The wetting of PDMS-grafted silica spheres (PDMS- g-silica) is connected to their depletion restabilization in semidilute and concentrated PDMS/cyohexane polymer solutions. Specifically, we found that a wetting diagram of chemically identical graft and free homopolymers predicts stability of hard, semisoft, and soft spheres as a function of the bulk free polymer volume fraction, graft density, and the graft and free polymer chain lengths. The transition between stable and aggregated regions is determined optically and with dynamic light scattering. The point of demarcation between the regions occurs when the graft and free polymer chains are equal in length. When graft chains are longer than free chains, the particles are stable; in contrast, the particles are unstable when the opposite is true. The regions of particle stability and instability are corroborated with theoretical self-consistent mean-field calculations, which not only show that the grafted brush is responsible for particle dispersion in the complete wetting region but also aggregation in the incomplete wetting region. Ultimately, our results indicate that depletion restabilization depends on the interfacial properties of the nanoparticles in semidilute and concentrated polymer solutions.

Abnormal viscoelastic behavior of side-chain liquid-crystal polymers

NASA Astrophysics Data System (ADS)

Gallani, J. L.; Hilliou, L.; Martinoty, P.; Keller, P.

1994-03-01

We show that, contrary to what is commonly believed, the isotropic phase of side-chain liquid-crystal polymers has viscoelastic properties which are totally different from those of ordinary flexible melt polymers. The results can be explained by the existence of a transient network created by the dynamic association of mesogenic groups belonging to different chains. The extremely high sensitivity of the compound to the state of the surfaces with which it is in contact offers us an unexpected method of studying surface states.

Numerical investigation of electron localization in polymer chains

NASA Astrophysics Data System (ADS)

Paulsson, Magnus; Stafström, Sven

1998-01-01

Using finite-size scaling, we have calculated the localization-delocalization phase diagrams for electronic wave functions in different disordered polymeric systems. The disorder considered here simulates finite polymer chain lengths, breaks in the conjugation, and disorder in an external potential. It is shown that a system of interacting chains, even at rather weak interchain interactions, allows for enough flexibility for the scattered waves to avoid dephasing and localization. Localization and the metal-insulator transition in highly conducting polymers are discussed in view of these results.

Self-consistent field theory and numerical scheme for calculating the phase diagram of wormlike diblock copolymers

NASA Astrophysics Data System (ADS)

Jiang, Ying; Chen, Jeff Z. Y.

2013-10-01

This paper concerns establishing a theoretical basis and numerical scheme for studying the phase behavior of AB diblock copolymers made of wormlike chains. The general idea of a self-consistent field theory is the combination of the mean-field approach together with a statistical weight that describes the configurational properties of a polymer chain. In recent years, this approach has been extensively used for structural prediction of block copolymers, based on the Gaussian-model description of a polymer chain. The wormlike-chain model has played an important role in the description of polymer systems, covering the semiflexible-to-rod crossover of the polymer properties and the highly stretching regime, which the Gaussian-chain model has difficulties to describe. Although the idea of developing a self-consistent field theory for wormlike chains could be traced back to early development in polymer physics, the solution of such a theory has been limited due to technical difficulties. In particular, a challenge has been to develop a numerical algorithm enabling the calculation of the phase diagram containing three-dimensional structures for wormlike AB diblock copolymers. This paper describes a computational algorithm that combines a number of numerical tricks, which can be used for such a calculation. A phase diagram covering major parameter areas was constructed for the wormlike-chain system and reported by us, where the ratio between the total length and the persistence length of a constituent polymer is suggested as another tuning parameter for the microphase-separated structures; all detailed technical issues are carefully addressed in the current paper.

Molecular Design of Antifouling Polymer Brushes Using Sequence-Specific Peptoids

DOE PAGES

Lau, King Hang Aaron; Sileika, Tadas S.; Park, Sung Hyun; ...

2014-11-26

Material systems that can be used to flexibly and precisely define the chemical nature and molecular arrangement of a surface would be invaluable for the control of complex biointerfacial interactions. For example, progress in antifouling polymer biointerfaces that prevents nonspecific protein adsorption and cell attachment, which can significantly improve the performance of an array of biomedical and industrial applications, is hampered by a lack of chemical models to identify the molecular features conferring their properties. Poly(N-substituted glycine) “peptoids” are peptidomimetic polymers that can be conveniently synthesized with specific monomer sequences and chain lengths, and are presented as a versatile platformmore » for investigating the molecular design of antifouling polymer brushes. Zwitterionic antifouling polymer brushes have captured significant recent attention, and a targeted library of zwitterionic peptoid brushes with different charge densities, hydration, separations between charged groups, chain lengths, and grafted chain densities, is quantitatively evaluated for their antifouling properties through a range of protein adsorption and cell attachment assays. Specific zwitterionic brush designs are found to give rise to distinct but subtle differences in properties. In conclusion, the results also point to the dominant roles of the grafted chain density and chain length in determining the performance of antifouling polymer brushes.« less

Influence of the molecular architecture on the adsorption onto solid surfaces: comb-like polymers.

PubMed

Guzmán, Eduardo; Ortega, Francisco; Prolongo, Margarita G; Starov, Victor M; Rubio, Ramón G

2011-09-28

The processes of adsorption of grafted copolymers onto negatively charged surfaces were studied using a dissipative quartz crystal microbalance (D-QCM) and ellipsometry. The control parameters in the study of the adsorption are the existence or absence on the molecular architecture of grafted polyethyleneglycol (PEG) chains with different lengths and the chemical nature of the main chain, poly(allylamine) (PAH) or poly(L-lysine) (PLL). It was found out that the adsorption kinetics of the polymers showed a complex behavior. The total adsorbed amount depends on the architecture of the polymer chains (length of the PEG chains), on the polymer concentration and on the chemical nature of the main chain. The comparison of the thicknesses of the adsorbed layers obtained from D-QCM and from ellipsometry allowed calculation of the water content of the layers that is intimately related to the grafting length. The analysis of D-QCM results also provides information about the shear modulus of the layers, whose values have been found to be typical of a rubber-like polymer system. It is shown that the adsorption of polymers with a charged backbone is not driven exclusively by the electrostatic interactions, but the entropic contributions as a result of the trapping of water in the layer structure are of fundamental importance.

Longitudinal relaxation of initially straight flexible and stiff polymers

NASA Astrophysics Data System (ADS)

Dimitrakopoulos, Panagiotis; Dissanayake, Inuka

2004-11-01

The present talk considers the relaxation of a single flexible or stiff polymer chain from an initial straight configuration in a viscous solvent. This problem commonly arises when strong flows are turned off in both industrial and biological applications. The problem is also motivated by recent experiments with single biopolymer molecules relaxing after being fully extended by applied forces as well as by the recent development of micro-devices involving stretched tethered biopolymers. Our results are applicable to a wide array of synthetic polymers such as polyacrylamides, Kevlar and polyesters as well as biopolymers such as DNA, actin filaments, microtubules and MTV. In this talk we discuss the mechanism of the polymer relaxation as was revealed through Brownian Dynamics simulations covering a broad range of time scales and chain stiffness. After the short-time free diffusion, the chain's longitudinal reduction at early intermediate times is shown to constitute a universal behavior for any chain stiffness caused by a quasi-steady relaxation of tensions associated with the deforming action of the Brownian forces. Stiff chains are shown to exhibit a late intermediate-time longitudinal reduction associated with a relaxation of tensions affected by the deforming Brownian and the restoring bending forces. The longitudinal and transverse relaxations are shown to obey different laws, i.e. the chain relaxation is anisotropic at all times. In the talk, we show how from the knowledge of the relaxation mechanism, we can predict and explain the polymer properties including the polymer stress and the solution birefringence. In addition, a generalized stress-optic law is derived valid for any time and chain stiffness. All polymer properties which depend on the polymer length are shown to exhibit two intermediate-time behaviors with the early one to constitute a universal behavior for any chain stiffness. This work was supported in part by the Minta Martin Research Fund. The computations were performed on multiprocessor computers provided by the National Center for Supercomputing Applications (NCSA) in Illinois (grant DMR000003), and by an Academic Equipment Grant from Sun Microsystems Inc.

The Ultrasensitivity of Living Polymers

NASA Astrophysics Data System (ADS)

O'Shaughnessy, Ben; Vavylonis, Dimitrios

2003-03-01

Synthetic and biological living polymers are self-assembling chains whose chain length distributions (CLDs) are dynamic. We show these dynamics are ultrasensitive: Even a small perturbation (e.g., temperature jump) nonlinearly distorts the CLD, eliminating or massively augmenting short chains. The origin is fast relaxation of mass variables (mean chain length, monomer concentration) which perturbs CLD shape variables before these can relax via slow chain growth rate fluctuations. Viscosity relaxation predictions agree with experiments on the best-studied synthetic system, α-methylstyrene.

Universal scaling for polymer chain scission in turbulence

PubMed Central

Vanapalli, Siva A.; Ceccio, Steven L.; Solomon, Michael J.

2006-01-01

We report that previous polymer chain scission experiments in strong flows, long analyzed according to accepted laminar flow scission theories, were in fact affected by turbulence. We reconcile existing anomalies between theory and experiment with the hypothesis that the local stress at the Kolmogorov scale generates the molecular tension leading to polymer covalent bond breakage. The hypothesis yields a universal scaling for polymer scission in turbulent flows. This surprising reassessment of over 40 years of experimental data simplifies the theoretical picture of polymer dynamics leading to scission and allows control of scission in commercial polymers and genomic DNA. PMID:17075043

The Ultra-filtration of Macromolecules with Different Conformations and Configurations through Nanopores

NASA Astrophysics Data System (ADS)

Ge, Hui

This Ph. D. thesis presents our study on the ultrafiltration of polymers with different configurations and conformations; namly, theoretically, the passing of polymer chains through a nanopore under an elongational flow filed has been studied for years, but experimental studies are rare because of two following reasons: (1) lacks a precise method to investigate how individual single polymer chain pass through a nanopore; (2) it is difficult, if not impossible, to obtain a set of polymer samples with a narrow molar mass distribution and a uniform structures; except for linear chains. The central question in this study is to find the critical (minimum) flow rate (qc) for each kind of chains, at which the chains can pass through a given nanopore. A comparison of the measured and calculated qc leads to a better understanding how different chains are deformed, stretched and pulled through a nanopore. We have developed a novel method of combinating static and dynamic laser light scattering (LLS) to precisely measure the relative retention concentration ((C0 - C)/C0). Chapter 1 briefly introduces the theoretical background of how applications and lists some of resent research progresses in this area. Polymer with various configurations and conformations pass through nanopores; including polymer linear chains, stars polymer, branched polymers, polymer micelles are introduced. Among them, the de Gennes and Brochard-Wyart's predictions of polymer linear and star chains passing through nanopores are emphasized, in which they predicted that qc of linear chain is qc ≃ kBT/(3pieta), where kB, T and eta are the Boltzmann constant, the absolutely temperature, and the viscosity of solvent, respectively, independent of both the chain length and the pore size; and for star chains passing through nanopores, there exist a optimal entering arm numbers, namely, the star chains passing through nanopores. Chapter 2 details basic theory of static and dynamic laser light scattering (LLS), including its instrumentation and our ultrafiltration setup. Chapter 3 briefly introduces the sample preparation, including the history and mechanism of anionic living polymerization, as well as how we used a novel home-made set-up to prepare linear polystyrene with different chain lengths and star polystyrene with various arm numbers and lengths. Chapter 4 summarizes our measured critical flow rates (qc) of linear polymer chains with different lengths for nanopores with different sizes, since the flow rate is directly related to the hydrodynamic force, we have developed a sensitive method (down to tens fN) to directly assess how much the hydrodynamic force (Fh) is required to overcome the weak entropy elasticity and stretch individual coiled chains in solution. Our method is completely different from the using existing optical tweezers or AFM, because they measure the relatively stronger enthalpy elasticity. Our results confirm that qc is indeed independent of the chain length, but decreases as the pore size increases. The value of qc is ˜10--200 times smaller than kBT/(3pieta). Such a discrepancy has been attributed to the rough assumption made by de Gennes and his coworkers; namely, each chain segment "blob" confined inside the pore is not a hard sphere so that the effective length along the flow direction is much longer than the pore diameter. Finally, using the solution temperature, we varied the chain conformation, our result shows that q c has a minimum which is near, but not exactly located at the theta temperature, might leading to a better way to determine the true ideal state of a polymer solution, at which all viral coefficients, not only the second vanish. Chapter 5 uses polymer solutions made of different mixtures of linear and star chains, we have demonstrated that flushing these solution mixtures through a nanopore with a properly chosen flow rate can effectively and cleanly separate linear and star chains no matter whether linear chains are larger or smaller than star chains. Chapter 6 further investigates how star-like polystyrene pass through a given nanopore under the flow field. Star polystyrene chains with different arm lengths (LA) and numbers (f) passing through a nanopore (20 nm) under an elongational flow field was investigated in terms of the flow-rate dependent relative retention ((C0 - C)/C0), where C 0 and C are the polymer concentrations before and after the ultrafiltration. Our results reveal that for a given arm length (LA), the critical flow rate (qc,star), below which star chains are blocked, dramatically increases with the total arm numbers (f); but for a given f, is nearly independent on LA, contradictory to the previous prediction made by de Gennes and Brochard-Wyart. We have revised their theory in the region fin < fout and also accounted for the effective length of each blob, where fin and fout are the numbers of arms inside and outside the pore, respectively. In the revision, we show that qc,star is indeed independent of LA but related to f and f in in two different ways, depending on whether fin ≤ f/2 or ≥ f/2. A comparison of our experimental and calculated results reveals that most of star chains pass through the nanopores with fin ˜ f/2. Further study of the temperature dependent (C0 - C)/C 0 of polystyrene in cyclohexane reveals that there exists a minimum of qc,star at ˜38 °C, close to its theta temperature (-34.5 °C).

Dispersions of polymer ionomers: I.

PubMed

Capek, Ignác

2004-12-31

The principal subject discussed in the current paper is the effect of ionic functional groups in polymers on the formation of nontraditional polymer materials, polymer blends or polymer dispersions. Ionomers are polymers that have a small amount of ionic groups distributed along a nonionic hydrocarbon chain. Specific interactions between components in a polymer blend can induce miscibility of two or more otherwise immiscible polymers. Such interactions include hydrogen bonding, ion-dipole interactions, acid-base interactions or transition metal complexation. Ion-containing polymers provide a means of modifying properties of polymer dispersions by controlling molecular structure through the utilization of ionic interactions. Ionomers having a relatively small number of ionic groups distributed usually along nonionic organic backbone chains can agglomerate into the following structures: (1) multiplets, consisting of a small number of tightly packed ion pairs; and (2) ionic clusters, larger aggregates than multiplets. Ionomers exhibit unique solid-state properties as a result of strong associations among ionic groups attached to the polymer chains. An important potential application of ionomers is in the area of thermoplastic elastomers, where the associations constitute thermally reversible cross-links. The ionic (anionic, cationic or polar) groups are spaced more or less randomly along the polymer chain. Because in this type of ionomer an anionic group falls along the interior of the chain, it trails two hydrocarbon chain segments, and these must be accommodated sterically within any domain structure into which the ionic group enters. The primary effects of ionic functionalization of a polymer are to increase the glass transition temperature, the melt viscosity and the characteristic relaxation times. The polymer microstructure is also affected, and it is generally agreed that in most ionomers, microphase-separated, ion-rich aggregates form as a result of strong ion-dipole attractions. As a consequence of this new phase, additional relaxation processes are often observed in the viscoelastic behavior of ionomers. Light functionalization of polymers can increase the glass transition temperature and gives rise to two new features in viscoelastic behavior: (1) a rubbery plateau above T(g) and (2) a second loss process at elevated temperatures. The rubbery plateau was due to the formation of a physical network. The major effect of the ionic aggregate was to increase the longer time relaxation processes. This in turn increases the melt viscosity and is responsible for the network-like behavior of ionomers above the glass transition temperature. Ionomers rich in polar groups can fulfill the criteria for the self-assembly formation. The reported phenomenon of surface micelle formation has been found to be very general for these materials.

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

PubMed

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

2016-11-29

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

Chemically Realistic Tetrahedral Lattice Models for Polymer Chains: Application to Polyethylene Oxide.

PubMed

Dietschreit, Johannes C B; Diestler, Dennis J; Knapp, Ernst W

2016-05-10

To speed up the generation of an ensemble of poly(ethylene oxide) (PEO) polymer chains in solution, a tetrahedral lattice model possessing the appropriate bond angles is used. The distance between noncovalently bonded atoms is maintained at realistic values by generating chains with an enhanced degree of self-avoidance by a very efficient Monte Carlo (MC) algorithm. Potential energy parameters characterizing this lattice model are adjusted so as to mimic realistic PEO polymer chains in water simulated by molecular dynamics (MD), which serves as a benchmark. The MD data show that PEO chains have a fractal dimension of about two, in contrast to self-avoiding walk lattice models, which exhibit the fractal dimension of 1.7. The potential energy accounts for a mild hydrophobic effect (HYEF) of PEO and for a proper setting of the distribution between trans and gauche conformers. The potential energy parameters are determined by matching the Flory radius, the radius of gyration, and the fraction of trans torsion angles in the chain. A gratifying result is the excellent agreement of the pair distribution function and the angular correlation for the lattice model with the benchmark distribution. The lattice model allows for the precise computation of the torsional entropy of the chain. The generation of polymer conformations of the adjusted lattice model is at least 2 orders of magnitude more efficient than MD simulations of the PEO chain in explicit water. This method of generating chain conformations on a tetrahedral lattice can also be applied to other types of polymers with appropriate adjustment of the potential energy function. The efficient MC algorithm for generating chain conformations on a tetrahedral lattice is available for download at https://github.com/Roulattice/Roulattice .

An atomic finite element model for biodegradable polymers. Part 2. A model for change in Young's modulus due to polymer chain scission.

PubMed

Gleadall, Andrew; Pan, Jingzhe; Kruft, Marc-Anton

2015-11-01

Atomic simulations were undertaken to analyse the effect of polymer chain scission on amorphous poly(lactide) during degradation. Many experimental studies have analysed mechanical properties degradation but relatively few computation studies have been conducted. Such studies are valuable for supporting the design of bioresorbable medical devices. Hence in this paper, an Effective Cavity Theory for the degradation of Young's modulus was developed. Atomic simulations indicated that a volume of reduced-stiffness polymer may exist around chain scissions. In the Effective Cavity Theory, each chain scission is considered to instantiate an effective cavity. Finite Element Analysis simulations were conducted to model the effect of the cavities on Young's modulus. Since polymer crystallinity affects mechanical properties, the effect of increases in crystallinity during degradation on Young's modulus is also considered. To demonstrate the ability of the Effective Cavity Theory, it was fitted to several sets of experimental data for Young's modulus in the literature. Copyright © 2015 Elsevier Ltd. All rights reserved.

Nanoprobe diffusion in entangled polymer solutions: Linear vs. unconcatenated ring chains

NASA Astrophysics Data System (ADS)

Nahali, Negar; Rosa, Angelo

2018-05-01

We employ large-scale molecular dynamics computer simulations to study the problem of nanoprobe diffusion in entangled solutions of linear polymers and unknotted and unconcatenated circular (ring) polymers. By tuning both the diameter of the nanoprobe and the density of the solution, we show that nanoprobes of diameter smaller than the entanglement distance (tube diameter) of the solution display the same (Rouse-like) behavior in solutions of both polymer architectures. Instead, nanoprobes with larger diameters appear to diffuse markedly faster in solutions of rings than in solutions of linear chains. Finally, by analysing the distribution functions of spatial displacements, we find that nanoprobe motion in rings' solutions shows both Gaussian and ergodic behaviors, in all regimes considered, while, in solutions of linear chains, nanoprobes exceeding the size of the tube diameter show a transition to non-Gaussian and non-ergodic motion. Our results emphasize the role of chain architecture in the motion of nanoprobes dispersed in polymer solutions.

Solution-Phase Conformation and Dynamics of Conjugated Isoindigo-Based Donor–Acceptor Polymer Single Chains

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lee, Franklin L.; Farimani, Amir Barati; Gu, Kevin L.

Conjugated polymers are the key material in thin-film organic optoelectronic devices due to the versatility of these molecules combined with their semiconducting properties. A molecular-scale understanding of conjugated polymers is important to the optimization of the thin-film morphology. We examine the solution-phase behavior of conjugated isoindigo-based donor–acceptor polymer single chains of various chain lengths using atomistic molecular dynamics simulations. Our simulations elucidate the transition from a rod-like to a coil-like conformation from an analysis of normal modes and persistence length. In addition, we find another transition based on the solvent environment, contrasting the coil-like conformation in a good solvent withmore » a globule-like conformation in a poor solvent. Altogether, our results provide valuable insights into the transition between conformational regimes for conjugated polymers as a function of both the chain length and the solvent environment, which will help to accurately parametrize higher level models.« less

Solution-Phase Conformation and Dynamics of Conjugated Isoindigo-Based Donor–Acceptor Polymer Single Chains

DOE PAGES

Lee, Franklin L.; Farimani, Amir Barati; Gu, Kevin L.; ...

2017-10-25

Conjugated polymers are the key material in thin-film organic optoelectronic devices due to the versatility of these molecules combined with their semiconducting properties. A molecular-scale understanding of conjugated polymers is important to the optimization of the thin-film morphology. We examine the solution-phase behavior of conjugated isoindigo-based donor–acceptor polymer single chains of various chain lengths using atomistic molecular dynamics simulations. Our simulations elucidate the transition from a rod-like to a coil-like conformation from an analysis of normal modes and persistence length. In addition, we find another transition based on the solvent environment, contrasting the coil-like conformation in a good solvent withmore » a globule-like conformation in a poor solvent. Altogether, our results provide valuable insights into the transition between conformational regimes for conjugated polymers as a function of both the chain length and the solvent environment, which will help to accurately parametrize higher level models.« less

Configurations and Dynamics of Semi-Flexible Polymers in Good and Poor Solvents

NASA Astrophysics Data System (ADS)

Larson, Ronald

We develop coarse-graining procedures for determining the conformational and dynamic behavior of semi-flexible chains with and without flow using Brownian dynamics (BD) simulations that are insensitive to the degree of coarse-graining. In the absence of flow, in a poor solvent, we find three main collapsed states: torus, bundle, and globule over a range of dimensionless ratios of the three energy parameters, namely solvent-polymer surface energy, energy of polymer folds, and polymer bending energy or persistence length. A theoretical phase diagram, confirmed by BD simulations, captures the general phase behavior of a single long chain (>10 Kuhn lengths) at moderately high (order unity) dimensionless temperature, which is the ratio of thermal energy to the attractive interaction between neighboring monomers. We also find converged results for polymer conformations in shear or extensional flow in solvents of various qualities and determine scaling laws for chain dimensions for low, moderate, and high Weissenberg numbers Wi. We also derive scaling laws to describe chains dimensions and tumbling rates in these regimes.

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

PubMed Central

Piwoński, Hubert; Michinobu, Tsuyoshi; Habuchi, Satoshi

2017-01-01

Applications of conjugated polymer nanoparticles (Pdots) for imaging and sensing depend on their size, fluorescence brightness and intraparticle energy transfer. The molecular design of conjugated polymers (CPs) has been the main focus of the development of Pdots. Here we demonstrate that proper control of the physical interactions between the chains is as critical as the molecular design. The unique design of twisted CPs and fine-tuning of the reprecipitation conditions allow us to fabricate ultrasmall (3.0–4.5 nm) Pdots with excellent photostability. Extensive photophysical and structural characterization reveals the essential role played by the packing of the polymer chains in the particles in the intraparticle spatial alignment of the emitting sites, which regulate the fluorescence brightness and the intraparticle energy migration efficiency. Our findings enhance understanding of the relationship between chain interactions and the photophysical properties of CP nanomaterials, providing a framework for designing and fabricating functional Pdots for imaging applications. PMID:28508857

Self-assembly and glass-formation in a lattice model of telechelic polymer melts: Influence of stiffness of the sticky bonds

DOE Office of Scientific and Technical Information (OSTI.GOV)

Xu, Wen-Sheng, E-mail: wsxu@uchicago.edu; Freed, Karl F., E-mail: freed@uchicago.edu; Department of Chemistry, The University of Chicago, Chicago, Illinois 60637

2016-06-07

Telechelic polymers are chain macromolecules that may self-assemble through the association of their two mono-functional end groups (called “stickers”). A deep understanding of the relation between microscopic molecular details and the macroscopic physical properties of telechelic polymers is important in guiding the rational design of telechelic polymer materials with desired properties. The lattice cluster theory (LCT) for strongly interacting, self-assembling telechelic polymers provides a theoretical tool that enables establishing the connections between important microscopic molecular details of self-assembling polymers and their bulk thermodynamics. The original LCT for self-assembly of telechelic polymers considers a model of fully flexible linear chains [J.more » Dudowicz and K. F. Freed, J. Chem. Phys. 136, 064902 (2012)], while our recent work introduces a significant improvement to the LCT by including a description of chain semiflexibility for the bonds within each individual telechelic chain [W.-S. Xu and K. F. Freed, J. Chem. Phys. 143, 024901 (2015)], but the physically associative (or called “sticky”) bonds between the ends of the telechelics are left as fully flexible. Motivated by the ubiquitous presence of steric constraints on the association of real telechelic polymers that impart an additional degree of bond stiffness (or rigidity), the present paper further extends the LCT to permit the sticky bonds to be semiflexible but to have a stiffness differing from that within each telechelic chain. An analytical expression for the Helmholtz free energy is provided for this model of linear telechelic polymer melts, and illustrative calculations demonstrate the significant influence of the stiffness of the sticky bonds on the self-assembly and thermodynamics of telechelic polymers. A brief discussion is also provided for the impact of self-assembly on glass-formation by combining the LCT description for this extended model of telechelic polymers with the Adam-Gibbs relation between the structural relaxation time and the configurational entropy.« less

Prediction of Solution Properties of Flexible-Chain Polymers: A Computer Simulation Undergraduate Experiment

ERIC Educational Resources Information Center

de la Torre, Jose Garcia; Cifre, Jose G. Hernandez; Martinez, M. Carmen Lopez

2008-01-01

This paper describes a computational exercise at undergraduate level that demonstrates the employment of Monte Carlo simulation to study the conformational statistics of flexible polymer chains, and to predict solution properties. Three simple chain models, including excluded volume interactions, have been implemented in a public-domain computer…

DOE Office of Scientific and Technical Information (OSTI.GOV)

Liu, Siqi; Senses, Erkan; Jiao, Yang

Nanoparticles functionalized with long polymer chains at low graft density are interesting systems to study structure–dynamic relationships in polymer nanocomposites since they are shown to aggregate into strings in both solution and melts and also into spheres and branched aggregates in the presence of free polymer chains. Our work investigates structure and entanglement effects in composites of polystyrene-grafted iron oxide nanoparticles by measuring particle relaxations using X-ray photon correlation spectroscopy. And for particles within highly ordered strings and aggregated systems, they experience a dynamically heterogeneous environment displaying hyperdiffusive relaxation commonly observed in jammed soft glassy systems. Furthermore, particle dynamics ismore » diffusive for branched aggregated structures which could be caused by less penetration of long matrix chains into brushes. These results suggest that particle motion is dictated by the strong interactions of chains grafted at low density with the host matrix polymer.« less

Test of the ``radical-like polymerization'' scheme in molecular dynamics on the behavior of polymers under shock loading

NASA Astrophysics Data System (ADS)

Lemarchand, Claire; Bousquet, David; Schnell, Benoît; Pineau, Nicolas

2017-06-01

The behavior of polymer melts under shock loading is a question attracting more and more attention because of applications such as polymer-bonded explosives, light-weight armor and civilian protective equipment, like sports and car equipment. Molecular dynamics (MD) simulations are a very good tool to characterize the microscopic response of the polymer to a shock wave. To do so, the initial configuration of the polymer melt needs to be realistic. The ``radical-like polymerization'' scheme is a method to obtain near equilibrium configurations of a melt of long polymer chains. It consists in adding one neighboring monomer at a time to each growing chain. Between each polymerization step an MD run is performed to relax the new configuration. We test how details of our implementation of the ``radical-like polymerization'' scheme can impact or not Hugoniot curves and changes of chain configuration under shock. We compare our results to other simulation and experimental results on reference polymers.

Synthesis of surface-anchored DNA-polymer bioconjugates using reversible addition-fragmentation chain transfer polymerization.

PubMed

He, Peng; He, Lin

2009-07-13

We report here an approach to grafting DNA-polymer bioconjugates on a planar solid support using reversible addition-fragmentation chain transfer (RAFT) polymerization. In particular, a trithiocarbonate compound as the RAFT chain transfer agent (CTA) is attached to the distal point of a surface-immobilized oligonucleotide. Initiation of RAFT polymerization leads to controlled growth of polymers atop DNA molecules on the surface. Growth kinetics of poly(monomethoxy-capped oligo(ethylene glycol) methacrylate) atop DNA molecules is investigated by monitoring the change of polymer film thickness as a function of reaction time. The reaction conditions, including the polymerization temperature, the initiator concentration, the CTA surface density, and the selection of monomers, are varied to examine their impacts on the grafting efficiency of DNA-polymer conjugates. Comparing to polymer growth atop small molecules, the experimental results suggest that DNA molecules significantly accelerate polymer growth, which is speculated as a result of the presence of highly charged DNA backbones and purine/pyrimidine moieties surrounding the reaction sites.

Membrane consisting of polyquaternary amine ion exchange polymer network interpenetrating the chains of thermoplastic matrix polymer

NASA Technical Reports Server (NTRS)

Rembaum, A.; Wallace, C. J. (Inventor)

1978-01-01

An ion exchange membrane was formed from a solution containing dissolved matrix polymer and a set of monomers which are capable of reacting to form a polyquaternary ion exchange material; for example vinyl pyride and a dihalo hydrocarbon. After casting solution and evaporation of the volatile component's, a relatively strong ion exchange membrane was obtained which is capable of removing anions, such as nitrate or chromate from water. The ion exchange polymer forms an interpenetrating network with the chains of the matrix polymer.

3-D Particle Simulation of Strongly-Coupled Chains of Charged Polymers

NASA Astrophysics Data System (ADS)

Tanaka, Toyoichi; Tanaka, Motohiko; Pande, V.; Grosberg, A.

1996-11-01

The behaviors of the polyampholyte (PA) which is a connected chain of charged beads (molecules) submerged in the neutral solvent is studied using the 3-D particle simulation code. The major issue is how an equilibrium and kinetics of the PA depend on the thermal and electrostatic forces, i.e., the coupling constant Γ= e^2/aT . We follow a dynamical evolution of the PA, considering the electrostatic force, (2) the binding force between the adjacent beads, (3) the random thermal force exerted by the solvent, and (4) the frictional force: m fracdv_idt = sumj fracZ_iZj e^2 |ri -r_j|^2 hatr_ij - frac3Ta^2(2 ri -r_i+1 -r_i-1) + F^(th) - m ν v_i. Preliminary runs show that, when the excess charge δ N on the chain is larger than N^1/2 ( N : the number of the beads), the size of the polyampholyte increases as in the Monte Carlo simulation using the energy principle [Kantor, Kardar and Li, Phys.Rev.E, 49, 1383 (1994)]. The measured time rate of the size increase for the fixed value of Γ is scaled as, d/dt ~ δ N - N^1/2 for δ N > N^1/2 , and d/dt ~ 0 otherwise.

Environmental barrier material for organic light emitting device and method of making

DOEpatents

Graff, Gordon L [West Richland, WA; Gross, Mark E [Pasco, WA; Affinito, John D [Kennewick, WA; Shi, Ming-Kun [Richland, WA; Hall, Michael [West Richland, WA; Mast, Eric [Richland, WA

2003-02-18

An encapsulated organic light emitting device. The device includes a first barrier stack comprising at least one first barrier layer and at least one first polymer layer. There is an organic light emitting layer stack adjacent to the first barrier stack. A second barrier stack is adjacent to the organic light emitting layer stack. The second barrier stack has at least one second barrier layer and at least one second polymer layer. A method of making the encapsulated organic light emitting device is also provided.

Single-polymer dynamics under constraints: scaling theory and computer experiment.

PubMed

Milchev, Andrey

2011-03-16

The relaxation, diffusion and translocation dynamics of single linear polymer chains in confinement is briefly reviewed with emphasis on the comparison between theoretical scaling predictions and observations from experiment or, most frequently, from computer simulations. Besides cylindrical, spherical and slit-like constraints, related problems such as the chain dynamics in a random medium and the translocation dynamics through a nanopore are also considered. Another particular kind of confinement is imposed by polymer adsorption on attractive surfaces or selective interfaces--a short overview of single-chain dynamics is also contained in this survey. While both theory and numerical experiments consider predominantly coarse-grained models of self-avoiding linear chain molecules with typically Rouse dynamics, we also note some recent studies which examine the impact of hydrodynamic interactions on polymer dynamics in confinement. In all of the aforementioned cases we focus mainly on the consequences of imposed geometric restrictions on single-chain dynamics and try to check our degree of understanding by assessing the agreement between theoretical predictions and observations.

Viscoplastic fracture transition of a biopolymer gel.

PubMed

Frieberg, Bradley R; Garatsa, Ray-Shimry; Jones, Ronald L; Bachert, John O; Crawshaw, Benjamin; Liu, X Michael; Chan, Edwin P

2018-06-13

Physical gels are swollen polymer networks consisting of transient crosslink junctions associated with hydrogen or ionic bonds. Unlike covalently crosslinked gels, these physical crosslinks are reversible thus enabling these materials to display highly tunable and dynamic mechanical properties. In this work, we study the polymer composition effects on the fracture behavior of a gelatin gel, which is a thermoreversible biopolymer gel consisting of denatured collagen chains bridging physical network junctions formed from triple helices. Below the critical volume fraction for chain entanglement, which we confirm via neutron scattering measurements, we find that the fracture behavior is consistent with a viscoplastic type process characterized by hydrodynamic friction of individual polymer chains through the polymer mesh to show that the enhancement in fracture scales inversely with the squared of the mesh size of the gelatin gel network. Above this critical volume fraction, the fracture process can be described by the Lake-Thomas theory that considers fracture as a chain scission process due to chain entanglements.

Mechanisms of chain adsorption on porous substrates and critical conditions of polymer chromatography.

PubMed

Cimino, Richard T; Rasmussen, Christopher J; Brun, Yefim; Neimark, Alexander V

2016-11-01

Polymer adsorption is a ubiquitous phenomenon with numerous technological and healthcare applications. The mechanisms of polymer adsorption on surfaces and in pores are complex owing to a competition between various entropic and enthalpic factors. Due to adsorption of monomers to the surface, the chain gains in enthalpy yet loses in entropy because of confining effects. This competition leads to the existence of critical conditions of adsorption when enthalpy gain and entropy loss are in balance. The critical conditions are controlled by the confining geometry and effective adsorption energy, which depends on the solvent composition and temperature. This phenomenon has important implications in polymer chromatography, since the retention at the critical point of adsorption (CPA) is chain length independent. However, the mechanisms of polymer adsorption in pores are poorly understood and there is an ongoing discussion in the theoretical literature about the very existence of CPA for polymer adsorption on porous substrates. In this work, we examine the mechanisms of chain adsorption on a model porous substrate using Monte Carlo (MC) simulations. We distinguish three adsorption mechanisms depending on the chain location: on external surface, completely confined in pores, and also partially confined in pores in so-called "flower" conformations. The free energies of different conformations of adsorbed chains are calculated by the incremental gauge cell MC method that allows one to determine the partition coefficient as a function of the adsorption potential, pore size, and chain length. We confirm the existence of the CPA for chain length independent separation on porous substrates, which is explained by the dominant contributions of the chain adsorption at the external surface, in particular in flower conformations. Moreover, we show that the critical conditions for porous and nonporous substrates are identical and depend only on the surface chemistry. The theoretical results are confirmed by comparison with experimental data on chromatographic separation of a series of linear polystyrenes. Copyright © 2016 Elsevier Inc. All rights reserved.

Role of special cross-links in structure formation of bacterial DNA polymer

NASA Astrophysics Data System (ADS)

Agarwal, Tejal; Manjunath, G. P.; Habib, Farhat; Lakshmi Vaddavalli, Pavana; Chatterji, Apratim

2018-01-01

Using data from contact maps of the DNA-polymer of Escherichia coli (E. Coli) (at kilobase pair resolution) as an input to our model, we introduce cross-links between monomers in a bead-spring model of a ring polymer at very specific points along the chain. Via suitable Monte Carlo simulations, we show that the presence of these cross-links leads to a particular organization of the chain at large (micron) length scales of the DNA. We also investigate the structure of a ring polymer with an equal number of cross-links at random positions along the chain. We find that though the polymer does get organized at the large length scales, the nature of the organization is quite different from the organization observed with cross-links at specific biologically determined positions. We used the contact map of E. Coli bacteria which has around 4.6 million base pairs in a single circular chromosome. In our coarse-grained flexible ring polymer model, we used 4642 monomer beads and observed that around 80 cross-links are enough to induce the large-scale organization of the molecule accounting for statistical fluctuations caused by thermal energy. The length of a DNA chain even of a simple bacterial cell such as E. Coli is much longer than typical proteins, hence we avoided methods used to tackle protein folding problems. We define new suitable quantities to identify the large scale structure of a polymer chain with a few cross-links.

Effect of molecular properties on the performance of polymer light-emitting diodes

NASA Astrophysics Data System (ADS)

Ramos, Marta M. D.; Almeida, A. M.; Correia, Helena M. G.; Ribeiro, R. Mendes; Stoneham, A. M.

2004-11-01

The performance of a single layer polymer light-emitting diode depends on several interdependent factors, although recombination between electrons and holes within the polymer layer is believed to play an important role. Our aim is to carry out computer experiments in which bipolar charge carriers are injected in polymer networks made of poly(p-phenylene vinylene) chains randomly oriented. In these simulations, we follow the charge evolution in time from some initial state to the steady state. The intra-molecular properties of the polymer molecules obtained from self-consistent quantum molecular dynamics calculations are used in the mesoscopic model. The purpose of the present work is to clarify the effects of intra-molecular charge mobility and energy disorder on recombination efficiency. In particular, we find that charge mobility along the polymer chains has a serious influence on recombination within the polymer layer. Our results also show that energy disorder due to differences in ionization potential and electron affinity of neighbouring molecules affects mainly recombinations that occur near the electrodes at polymer chains parallel to them.

Self-Consistent Field Theory of Gaussian Ring Polymers

NASA Astrophysics Data System (ADS)

Kim, Jaeup; Yang, Yong-Biao; Lee, Won Bo

2012-02-01

Ring polymers, being free from chain ends, have fundamental importance in understanding the polymer statics and dynamics which are strongly influenced by the chain end effects. At a glance, their theoretical treatment may not seem particularly difficult, but the absence of chain ends and the topological constraints make the problem non-trivial, which results in limited success in the analytical or semi-analytical formulation of ring polymer theory. Here, I present a self-consistent field theory (SCFT) formalism of Gaussian (topologically unconstrained) ring polymers for the first time. The resulting static property of homogeneous and inhomogeneous ring polymers are compared with the random phase approximation (RPA) results. The critical point for ring homopolymer system is exactly the same as the linear polymer case, χN = 2, since a critical point does not depend on local structures of polymers. The critical point for ring diblock copolymer melts is χN 17.795, which is approximately 1.7 times of that of linear diblock copolymer melts, χN 10.495. The difference is due to the ring structure constraint.

Nonlinear optical anisotropy and molecular orientational distribution in poly(p-phenylene benzobisthiazole) Langmuir-Blodgett films

NASA Astrophysics Data System (ADS)

Wang, Liming; Wada, Tatsuo; Yuba, Tomoyuki; Kakimoto, Masaaki; Imai, Yoshio; Sasabe, Hiroyuki

1996-06-01

The orientational distribution and packing of polymer chains were investigated in poly(p-phenylene benzobisthiazole) (PBT) Langmuir-Blodgett (LB) films by nonresonant third-harmonic generation measurement at a wavelength of 1907 nm. The tensor components of the third-harmonic susceptibility on the PBT LB film with a surface pressure of 50 mN/m were determined to be χ(3)XXXX=(16.6±2.5)×10-12 and χ(3)YYYY=(2.0±0.3)×10-12. The large nonlinear optical anisotropy can be explained as a result of highly oriented packing of the polymer chains induced by a flow orientation. A Gaussian distribution function with a standard deviation of σ=0.40 gives a practical description of the orientational distribution of PBT polymer chains. A maximum χ(3) value of (26.8±4.4)×10-12 esu is predicted assuming a perfect alignment of polymer chains. The χ(3)XXXX value increased by factor of 2 with the surface pressure from 30 to 50 mN/m mainly due to the packing density of the polymer chains, while the orientational degree did not change.

Surface properties of functional polymer systems

NASA Astrophysics Data System (ADS)

Wong, Derek

Polymer surface modification typically involves blending with other polymers or chemical modification of the parent polymer. Such strategies inevitably result in polymer systems that are spatially and chemically heterogeneous, and which exhibit the phenomenon of surface segregation. This work investigates the effects of chain architecture on the surface segregation behavior of such functionally modified polymers using a series of end- and center-fluorinated poly(D,L-lactide). Surface segregation of the fluorinated functional groups was observed in both chain architectures via AMPS and water contact angle. Higher surface segregation was noted for functional groups located at the chain end as opposed to those in the middle of the chain. A self-consistent mean-field lattice theory was used to model the composition depth profiles of functional groups and excellent agreement was found between the model predictions and the experimental AMPS data in both chain architectures. Polymer properties are also in general dependent on both time and temperature, and exhibit a range of relaxation times in response to environmental stimuli. This behavior arises from the characteristic frequencies of molecular motions of the polymer chain and the interrelationship between time and temperature has been widely established for polymer bulk properties. There is evidence that surface properties also respond in a manner that is time and temperature dependent and that this dependence may not be the same as that observed for bulk properties. AMPS and water contact angle experiments were used to investigate the surface reorganization behavior of functional groups using a series of anionically synthesized end-fluorinated and end-carboxylated poly(styrene). It was found that both types of functional end-groups reorganized upon a change in the polarity of the surface environment in order to minimize the surface free energy. ADXPS and contact angle results suggest that the reorganization depth was confined to the top 2--3 nm of the surface. Contact angle results showed also that the reorganization process proceeded as a function of (time) 1/2, indicating that it is likely diffusion controlled. The magnitudes of the activation energies determined from the experimental data according to the Arhenius equation, suggest that the process is possibly correlated with known bulk beta and gamma relaxations in the polymer.

Molecular Design for Preparation of Hexagonal-Ordered Porous Films Based on Side-chain Type Liquid-Crystalline Star Polymer.

PubMed

Naka, Yumiko; Takayama, Hiromu; Koyama, Teruhisa; Le, Khoa V; Sasaki, Takeo

2018-05-02

Fabrication of regularly porous films by the breath-figure method has attracted much attention. The simple, low-cost technique uses the condensation of water droplets to produce these structures, but the phenomenon itself is complex, requiring control over many interacting parameters that change throughout the process. Developing a unified understanding for the molecular design of polymers to prepare ordered porous films is challenging, but required for further advancements. In this article, the effects of the chemical structure of polymers in the breath-figure technique were systematically explored using side-chain type liquid-crystalline (LC) star polymers. The formation of porous films was affected by the structure of the polymers. Although the entire film surface of poly(11-[4-(4-cyanobiphenyl)oxy]undecyl methacrylate) (P11CB) had a hexagonal ordered porous structure over a certain Mn value, regularly arranged holes did not easily form in poly(methyl methacrylate) (PMMA), even though the main chain of PMMA is similar to that of P11CB. Comparing P11CB and poly(11-[(1,1'-biphenyl)-4-yloxy]undecyl methacrylate) (P11B) (P11CB without cyano groups) showed that the local polar groups in hydrophobic polymers promoted the formation of ordered porous films. No holes formed in poly(4-cyanobiphenyl methacrylate) (P0CB) (P11CB without alkyl spacers) films due to its hydrophilicity. The introduction of alkyl chains in P0CB allowed the preparation of honeycomb-structured films by increasing the internal tension. However, alkyl chains in the side chain alone did not result in a porous structure, as in the case of poly(11-[(1,1'-biphenyl)-4-yloxy]undecyl methacrylate) (P11). Aromatic rings are also required to increase the Tg and improve film formability. In the present study, suitable molecular designs of polymers were found, specifically hydrophobic polymers with local polar groups, to form a regularly porous structure. Development of clear guidelines for the molecular design of polymers is the subject of our current research, which will enable the fabrication of porous films using various functional polymers.

NMR (Nuclear Magnetic Resonance) and macromolecular migration in a melt or in concentrated solutions

NASA Technical Reports Server (NTRS)

Addad, J. P. C.

1983-01-01

The purpose of this paper is to analyze the migration process of long polymer molecules in a melt or in concentrated solutions as it may be observed from the dynamics of the transverse magnetization of nuclear spins linked to these chains. The low frequency viscoelastic relaxation of polymer systems is known to be mainly controlled by the mechanism of dissociation of topological constraints excited on chains and which are called entanglements. This mechanism exhibits a strong dependence upon the chain molecular weight. These topological constraints also govern the diffusion process of polymer chains. So, the accurate description of the diffusion motion of a chain may be a convenient way to characterize disentanglement processes necessarily involved in any model proposed to explain viscoelastic effects.

Structural Ordering of Semiconducting Polymers and Small-Molecules for Organic Electronics

NASA Astrophysics Data System (ADS)

O'Hara, Kathryn Allison

Semiconducting polymers and small-molecules can be readily incorporated into electronic devices such as organic photovoltaics (OPVs), thermoelectrics (OTEs), organic light emitting diodes (OLEDs), and organic thin film transistors (OTFTs). Organic materials offer the advantage of being processable from solution to form flexible and lightweight thin films. The molecular design, processing, and resulting thin film morphology of semiconducting polymers drastically affect the optical and electronic properties. Charge transport within films of semiconducting polymers relies on the nanoscale organization to ensure electronic coupling through overlap of molecular orbitals and to provide continuous transport pathways. While the angstrom-scale packing details can be studied using X-ray scattering methods, an understanding of the mesoscale, or the length scale over which smaller ordered regions connect, is much harder to achieve. Grain boundaries play an important role in semiconducting polymer thin films where the average grain size is much smaller than the total distance which charges must traverse in order to reach the electrodes in a device. The majority of semiconducting polymers adopt a lamellar packing structure in which the conjugated backbones align in parallel pi-stacks separated by the alkyl side-chains. Only two directions of transport are possible--along the conjugated backbone and in the pi-stacking direction. Currently, the discussion of transport between crystallites is centered around the idea of tie-chains, or "bridging" polymer chains connecting two ordered regions. However, as molecular structures become increasingly complex with the development of new donor-acceptor copolymers, additional forms of connectivity between ordered domains should be considered. High resolution transmission electron microscopy (HRTEM) is a powerful tool for directly imaging the crystalline grain boundaries in polymer and small-molecule thin films. Recently, structures comparable to quadrites were discovered in the semiconducting polymer, PSBTBT, where the angle of chain overlap could be predicted by the geometry of the backbone and alkyl side-chains. Such structures are hypothesized to improve the electronic connectivity and enable 3D transport. Now, it has been determined that another semiconducting polymer, PBDTTPD, forms cross-chain structures in thin films. PBDTTPD is a low band-gap donor-acceptor copolymer used in high efficiency OPVs. The effect of the alkyl side-chains on intercrystallite order is determined by examining three different derivatives of the PBDTTPD polymer with HRTEM. Additionally, the expansion and contraction of films during thermal annealing and slow cooling is monitored through in-situ grazing incidence wide-angle X-ray scattering (GIWAXS) measurements. Results show that minor variations in side-chain structure drive both crystallite orientation and the formation of crossed structures. Overall, these studies suggest design principles to continue to advance the field of organic electronics.

Dimension of ring polymers in bulk studied by Monte-Carlo simulation and self-consistent theory.

PubMed

Suzuki, Jiro; Takano, Atsushi; Deguchi, Tetsuo; Matsushita, Yushu

2009-10-14

We studied equilibrium conformations of ring polymers in melt over the wide range of segment number N of up to 4096 with Monte-Carlo simulation and obtained N dependence of radius of gyration of chains R(g). The simulation model used is bond fluctuation model (BFM), where polymer segments bear excluded volume; however, the excluded volume effect vanishes at N-->infinity, and linear polymer can be regarded as an ideal chain. Simulation for ring polymers in melt was performed, and the nu value in the relationship R(g) proportional to N(nu) is decreased gradually with increasing N, and finally it reaches the limiting value, 1/3, in the range of N>or=1536, i.e., R(g) proportional to N(1/3). We confirmed that the simulation result is consistent with that of the self-consistent theory including the topological effect and the osmotic pressure of ring polymers. Moreover, the averaged chain conformation of ring polymers in equilibrium state was given in the BFM. In small N region, the segment density of each molecule near the center of mass of the molecule is decreased with increasing N. In large N region the decrease is suppressed, and the density is found to be kept constant without showing N dependence. This means that ring polymer molecules do not segregate from the other molecules even if ring polymers in melt have the relationship nu=1/3. Considerably smaller dimensions of ring polymers at high molecular weight are due to their inherent nature of having no chain ends, and hence they have less-entangled conformations.

Syntheses, structures and luminescent properties of lanthanide coordination polymers assembled from imidazophenanthroline derivative and oxalate ligands

NASA Astrophysics Data System (ADS)

Zhao, Hui; Sun, Xiao-Xia; Hu, Huai-Ming; An, Ran; Yang, Meng-Lin; Xue, Ganglin

2017-01-01

Nine new lanthanide coordination polymers, namely, [Ln(Hsfpip)(ox)0.5(H2O)]n·2n(H2O) ((Ln=Eu (1), Tb (2), Dy (3), Ho (4), Er (5), Yb (6), Y(7)), [Ln(H2sfpip)(ox)(H2O)4]n·2n(H2O) (Ln=Nd (8) Sm (9)), [H2ox=oxalic acid， H3sfpip=2-(2,4-disulfophenyl)imidazo(4,5-f)(1,10)-phenanthroline] have been synthesized under hydrothermal conditions and characterized by IR spectra, elemental analysis, powder X-ray diffraction and single crystal X-ray diffraction. When sodium oxalate is added, the reactions of lanthanide ions with H3sfpip resulted in two types of structures. Compounds 1-7 are obtained at pH 5.0 and exhibit 3D tfz-d networks with ox2- anions as linkers to bridge the adjacent layers. Compounds 8-9 are obtained at pH 2.0, and display a 1D chain which is further extended to a 3D supramolecular framework through intermolecular hydrogen bonds and π-π interactions. The structural variation from compounds 1-7 to 8-9 can attribute to the pH effect on construction of lanthanide coordination polymers. Moreover, the thermal stabilities and luminescence properties of 1-9 were also investigated.

Atomistic simulation of graphene-based polymer nanocomposites

NASA Astrophysics Data System (ADS)

Rissanou, Anastassia N.; Bačová, Petra; Harmandaris, Vagelis

2016-05-01

Polymer/graphene nanostructured systems are hybrid materials which have attracted great attention the last years both for scientific and technological reasons. In the present work atomistic Molecular Dynamics simulations are performed for the study of graphene-based polymer nanocomposites composed of pristine, hydrogenated and carboxylated graphene sheets dispersed in polar (PEO) and nonpolar (PE) short polymer matrices (i.e., matrices containing chains of low molecular weight). Our focus is twofold; the one is the study of the structural and dynamical properties of short polymer chains and the way that they are affected by functionalized graphene sheets while the other is the effect of the polymer matrices on the behavior of graphene sheets.

Polymer relaxation and stretching dynamics in semi-dilute DNA solutions: a single molecule study

NASA Astrophysics Data System (ADS)

Hsiao, Kai-Wen; Brockman, Christopher; Schroeder, Charles

2015-03-01

In this work, we study polymer relaxation and stretching dynamics in semi-dilute DNA solutions using single molecule techniques. Using this approach, we uncover a unique scaling relation for longest polymer relaxation time that falls in the crossover regime described by semi-flexible polymer solutions, which is distinct from truly flexible polymer chains. In addition, we performed a series of step-strain experiments on single polymers in semi-dilute solutions in planar extensional flow using an automated microfluidic trap. In this way, we are able to precisely control the flow strength and the amount of strain applied to single polymer chains, thereby enabling direct observation of the full stretching and relaxation process in semi-dilute solutions during transient start-up and flow cessation. Interestingly, we observe polymer individualism in the conformation of single chains in semi-dilute solutions, which to our knowledge has not yet been observed. In addition, we observe the relaxation data can be explained by a multi-exponential decay process after flow cessation in semi-dilute solutions. Overall, our work reports key advance in non-dilute polymer systems from a molecular perspective via direct observation of dynamics in strong flows. DOW fellowship.

Structure of rigid polymers confined to nanoparticles: Molecular dynamics simulations insight

DOE PAGES

Maskey, Sabina; Lane, J. Matthew D.; Perahia, Dvora; ...

2016-02-04

Nanoparticles (NPs) grafted with organic layers form hybrids able to retain their unique properties through integration into the mesoscopic scale. The organic layer structure and response often determine the functionality of the hybrids on the mesoscopic length scale. Using molecular dynamics (MD) simulations, we probe the conformation of luminescent rigid polymers, dialkyl poly(p-phenylene ethynylene)s (PPE), end-grafted onto a silica nanoparticle in different solvents as the molecular weights and polymer coverages are varied. We find that, in contrast to NP-grafted flexible polymers, the chains are fully extended independent of the solvent. In toluene and decane, which are good solvents, the graftedmore » PPEs chains assume a similar conformation to that observed in dilute solutions. In water, which is a poor solvent for the PPEs, the polymer chains form one large cluster but remain extended. The radial distribution of the chains around the core of the nanoparticle is homogeneous in good solvents, whereas in poor solvents clusters are formed independent of molecular weights and coverages. As a result, the clustering is distinctively different from the response of grafted flexible and semiflexible polymers.« less

Sieving polymer synthesis by reversible addition fragmentation chain transfer polymerization.

PubMed

Nai, Yi Heng; Jones, Roderick C; Breadmore, Michael C

2013-12-01

Replaceable sieving polymers are the fundamental component for high resolution nucleic acids separation in CE. The choice of polymer and its physical properties play significant roles in influencing separation performance. Recently, reversible addition fragmentation chain transfer (RAFT) polymerization has been shown to be a versatile polymerization technique capable of yielding well defined polymers previously unattainable by conventional free radical polymerization. In this study, a high molecular weight PDMA at 765 000 gmol-1 with a PDI of 1.55 was successfully synthesized with the use of chain transfer agent - 2-propionic acidyl butyl trithiocarbonate (PABTC) in a multi-step sequential RAFT polymerization approach. This study represents the first demonstration of RAFT polymerization for synthesizing polymers with the molecular weight range suitable for high resolution DNA separation in sieving electrophoresis. Adjustment of pH in the reaction was found to be crucial for the successful RAFT polymerization of high molecular weight polymer as the buffered condition minimizes the effect of hydrolysis and aminolysis commonly associated with trithiocarbonate chain transfer agents. The separation efficiency of PABTC-PDMA was found to have marginally superior separation performance compared to a commercial PDMA formulation, POP™-CAP, of similar molecular weight range.

Analytical expressions for the closure probability of a stiff wormlike chain for finite capture radius.

PubMed

Guérin, T

2017-08-01

Estimating the probability that two monomers of the same polymer chain are close together is a key ingredient to characterize intramolecular reactions and polymer looping. In the case of stiff wormlike polymers (rigid fluctuating elastic rods), for which end-to-end encounters are rare events, we derive an explicit analytical formula for the probability η(r_{c}) that the distance between the chain extremities is smaller than some capture radius r_{c}. The formula is asymptotically exact in the limit of stiff chains, and it leads to the identification of two distinct scaling regimes for the closure factor, originating from a strong variation of the fluctuations of the chain orientation at closure. Our theory is compatible with existing analytical results from the literature that cover the cases of a vanishing capture radius and of nearly fully extended chains.

Buckling of paramagnetic chains in soft gels

NASA Astrophysics Data System (ADS)

Huang, Shilin; Pessot, Giorgio; Cremer, Peet; Weeber, Rudolf; Holm, Christian; Nowak, Johannes; Odenbach, Stefan; Menzel, Andreas M.; Auernhammer, Günter K.

We study the magneto-elastic coupling behavior of paramagnetic chains in soft polymer gels exposed to external magnetic fields. To this end, a laser scanning confocal microscope is used to observe the morphology of the paramagnetic chains together with the deformation field of the surrounding gel network. The paramagnetic chains in soft polymer gels show rich morphological shape changes under oblique magnetic fields, in particular a pronounced buckling deformation. The details of the resulting morphological shapes depend on the length of the chain, the strength of the external magnetic field, and the modulus of the gel. Based on the observation that the magnetic chains are strongly coupled to the surrounding polymer network, a simplified model is developed to describe their buckling behavior. A coarse-grained molecular dynamics simulation model featuring an increased matrix stiffness on the surfaces of the particles leads to morphologies in agreement with the experimentally observed buckling effects.

Simultaneous covalent and noncovalent hybrid polymerizations

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yu, Z.; Tantakitti, F.; Yu, T.

Covalent and supramolecular polymers are two distinct forms of soft matter, composed of long chains of covalently and noncovalently linked structural units, respectively. We report a hybrid system formed by simultaneous covalent and supramolecular polymerizations of monomers. The process yields cylindrical fibers of uniform diameter that contain covalent and supramolecular compartments, a morphology not observed when the two polymers are formed independently. The covalent polymer has a rigid aromatic imine backbone with helicoidal conformation, and its alkylated peptide side chains are structurally identical to the monomer molecules of supramolecular polymers. In the hybrid system, covalent chains grow to higher averagemore » molar mass relative to chains formed via the same polymerization in the absence of a supramolecular compartment. The supramolecular compartments can be reversibly removed and re-formed to reconstitute the hybrid structure, suggesting soft materials with novel delivery or repair functions.« less

Directionally Aligned Amorphous Polymer Chains via Electrohydrodynamic-Jet Printing: Analysis of Morphology and Polymer Field-Effect Transistor Characteristics.

PubMed

Kim, Yebyeol; Bae, Jaehyun; Song, Hyun Woo; An, Tae Kyu; Kim, Se Hyun; Kim, Yun-Hi; Park, Chan Eon

2017-11-15

Electrohydrodynamic-jet (EHD-jet) printing provides an opportunity to directly assembled amorphous polymer chains in the printed pattern. Herein, an EHD-jet printed amorphous polymer was employed as the active layer for fabrication of organic field-effect transistors (OFETs). Under optimized conditions, the field-effect mobility (μ FET ) of the EHD-jet printed OFETs was 5 times higher than the highest μ FET observed in the spin-coated OFETs, and this improvement was achieved without the use of complex surface templating or additional pre- or post-deposition processing. As the chain alignment can be affected by the surface energy of the dielectric layer in EHD-jet printed OFETs, dielectric layers with varying wettability were examined. Near-edge X-ray absorption fine structure measurements were performed to compare the amorphous chain alignment in OFET active layers prepared by EHD-jet printing and spin coating.

Interphase and particle dispersion correlations in polymer nanocomposites

NASA Astrophysics Data System (ADS)

Senses, Erkan

Particle dispersion in polymer matrices is a major parameter governing the mechanical performance of polymer nanocomposites. Controlling particle dispersion and understanding aging of composites under large shear and temperature variations determine the processing conditions and lifetime of composites which are very important for diverse applications in biomedicine, highly reinforced materials and more importantly for the polymer composites with adaptive mechanical responses. This thesis investigates the role of interphase layers between particles and polymer matrices in two bulk systems where particle dispersion is altered upon deformation in repulsive composites, and good-dispersion of particles is retained after multiple oscillatory shearing and aging cycles in attractive composites. We demonstrate that chain desorption and re-adsorption processes in attractive composites under shear can effectively enhance the bulk microscopic mechanical properties, and long chains of adsorbed layers lead to a denser entangled interphase layer. We further designed experiments where particles are physically adsorbed with bimodal lengths of homopolymer chains to underpin the entanglement effect in interphases. Bimodal adsorbed chains are shown to improve the interfacial strength and used to modulate the elastic properties of composites without changing the particle loading, dispersion state or polymer conformation. Finally, the role of dynamic asymmetry (different mobilities in polymer blends) and chemical heterogeneity in the interphase layer are explored in systems of poly(methyl methacrylate) adsorbed silica nanoparticles dispersed in poly(ethylene oxide) matrix. Such nanocomposites are shown to exhibit unique thermal-stiffening behavior at temperatures above glass transitions of both polymers. These interesting findings suggest that the mobility of the surface-bound polymer is essential for reinforcement in polymer nanocomposites, contrary to existing glassy layer theories for polymers on attractive particle surfaces. The shown thermally-induced stiffening behavior is reversible and makes this interfacial mechanism highly attractive in developing new active, remotely controllable engineered materials from non-responsive components.

Copolymer Synthesis and Characterization by Post-Polymerization Modification

NASA Astrophysics Data System (ADS)

Galvin, Casey James

This PhD thesis examines the physical behavior of surface-grafted polymer assemblies (SGPAs) derived from post-polymerization modification (PPM) reactions in aqueous and vapor enriched environments, and offers an alternative method of creating SGPAs using a PPM approach. SGPAs comprise typically polymer chains grafted covalently to solid substrates. These assemblies show promise in a number of applications and technologies due to the stability imparted by the covalent graft and ability to modify interfacial properties and stability. SGPAs also offer a set of rich physics to explore in fundamental investigations as a result of confining macromolecules to a solid substrate. PPM reactions (also called polymer analogous reactions) apply small molecule organic chemistry reactions to the repeat units of polymer chains in order to generate new chemistries. By applying a PPM strategy to SGPAs, a wide variety of functional groups can be introduced into a small number of well-studied and well-behaved model polymer systems. This approach offers the advantage of holding constant other properties of the SGPA (e.g., molecular weight, MW, and grafting density, sigma) to isolate the effect of chemistry on physical behavior. Using a combination of PPM and fabrication methods that facilitate the formation of SPGAs with position-dependent gradual variation of sigma on flat impenetrable substrate, the influence of polymer chemistry and sigma is examined on the stability of weak polyelectrolyte brushes in aqueous environments at different pH levels. Degrafting of polymer chains in SGPAs exhibits a complex dependence on side chain chemistry, sigma, pH and the charge fraction (alpha) within the brush. Results of these experiments support a proposed mechanism of degrafting, wherein extension of the grafted chains away from the substrate generates tension along the polymer backbone, which activates the grafting chemistry for hydrolysis. The implications of these findings are important in developing technologies that use SGPAs in aqueous environments, and point to a need for potential alternative grafting chemistries. The behavior of SGPAs in vapor environments remains an underexplored phenomenon. By changing systematically the chemistry of SGPAs derived from a parent sample, the influence of side chain functional groups on the swelling of weak and strong polyelectrolyte brushes in the presence of water, methanol and ethanol vapors is explored. The extent of swelling and solvent uptake depends strongly on the chemistry in the polymer side chain and of the solvent. Despite bearing a permanent electrostatic charge in the side chain, the strong polyelectrolyte brushes exhibit no behavior typical of polyelectrolytes in water due to no dissociation of the counterion. Of particular interest is the behavior in humid environments of an SGPA bearing a zwitterionic group in its side chain, which results in exposure of electrostatic charges without counterions. Using substrates bearing the aforementioned sigma gradient of polymeric grafts, evidence of inter- and intramolecular complex formation is presented. Finally, a method of developing SGPAs by polymerizing bulk polymer chains through surface-grafted monomers (SGMs) is described. The SGMs are incorporated onto a solid substrate using the same PPM reaction employed in the degrafting and vapor swelling experiments, highlighting the versatility of PPM. The thickness of these SGPAs is correlated to the bulk polymer chains MW, suggesting this technique can be used in existing industrial bulk polymerization processes.

Inhibition of the solid state transformation of carbamazepine in aqueous solution: impact of polymeric properties.

PubMed

Gift, Alan D; Hettenbaugh, Jacob A; Quandahl, Rachel A; Mapes, Madison

2017-11-06

The effects of polymers on the anhydrate-to-hydrate transformation of carbamazepine (CBZ) was investigated. The three types of polymers studied were polyvinylpyrrolidone (PVP), polyvinyl alcohol (PVA) and substituted celluloses which included hydroxypropyl methylcellulose (HPMC) and methylcellulose (MC). Anhydrous CBZ was added to dilute aqueous polymer solutions and Raman spectroscopy measurements were collected to monitor the kinetics of the solution-mediated transformation to CBZ dihydrate. Polymers exhibiting the greatest inhibition were able to reduce the growth phase of the solution-mediated transformation and change the habit of the hydrate crystal indicating polymer adsorption to the hydrate crystal surface as the mechanism of inhibition. The results of the various polymers showed that short chain substituted celluloses (HPMC and MC) inhibited the CBZ transformation to a much greater extent than longer chains. The same trend was observed for PVP and PVA, but to a lesser extent. These chain length effects were attributed to changes in polymer confirmation when adsorbed on the crystal surface. Additionally, decreasing the percentage of hydroxyl groups on the PVA polymer backbone reduced the ability of the polymer to inhibit the transformation and changing the degree of substitutions of methyl and hydroxypropyl groups on the cellulosic polymer backbone had no effect on the transformation.

Rare-event statistics and modular invariance

NASA Astrophysics Data System (ADS)

Nechaev, S. K.; Polovnikov, K.

2018-01-01

Simple geometric arguments based on constructing the Euclid orchard are presented, which explain the equivalence of various types of distributions that result from rare-event statistics. In particular, the spectral density of the exponentially weighted ensemble of linear polymer chains is examined for its number-theoretic properties. It can be shown that the eigenvalue statistics of the corresponding adjacency matrices in the sparse regime show a peculiar hierarchical structure and are described by the popcorn (Thomae) function discontinuous in the dense set of rational numbers. Moreover, the spectral edge density distribution exhibits Lifshitz tails, reminiscent of 1D Anderson localization. Finally, a continuous approximation for the popcorn function is suggested based on the Dedekind η-function, and the hierarchical ultrametric structure of the popcorn-like distributions is demonstrated to be related to hidden SL(2,Z) modular symmetry.

An easy and effective method to modulate molecular energy level of the polymer based on benzodithiophene for the application in polymer solar cells.

PubMed

Zhang, Maojie; Guo, Xia; Ma, Wei; Zhang, Shaoqing; Huo, Lijun; Ade, Harald; Hou, Jianhui

2014-04-02

Attaching meta-alkoxy-phenyl groups as conjugated side chains is an easy and effective way to modulate the molecular energy level of D-A polymer for photovoltaic application, and the polymer solar cells based on the polymer consisting meta-alkoxy-phenyl groups as conjugated side chain, PBT-OP, shows an enhanced open circuit voltage and thus higher efficiency of 7.50%, under the illumination of AM 1.5G, 100 mW/cm(2) . © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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 farther branched alkyl chains can effectively decrease interchain π-π stacking distance and improve carrier mobility. When we introduce electron-deficient functional groups on the isoindigo core, the LUMO levels of the polymers markedly decrease, which significantly improves the electron mobility and device stability. In addition, we present a new polymer system called BDOPV, which is based on the concept of π-extended isoindigo. By application of some strategies successfully used in isoindigo-based polymers, BDOPV-based polymers exhibit high mobility and good stability both in n-type and in ambipolar FETs. We believe that a synergy of molecular engineering strategies towards the isoindigo core, donor units, and side chains may further improve the performance and broaden the application of isoindigo-based polymers.

Well-defined block copolymers for gene delivery to dendritic cells: probing the effect of polycation chain-length.

PubMed

Tang, Rupei; Palumbo, R Noelle; Nagarajan, Lakshmi; Krogstad, Emily; Wang, Chun

2010-03-03

The development of safe and efficient polymer carriers for DNA vaccine delivery requires mechanistic understanding of structure-function relationship of the polymer carriers and their interaction with antigen-presenting cells. Here we have synthesized a series of diblock copolymers with well-defined chain-length using atom transfer radical polymerization and characterized the influence of polycation chain-length on the physico-chemical properties of the polymer/DNA complexes as well as the interaction with dendritic cells. The copolymers consist of a hydrophilic poly(ethylene glycol) block and a cationic poly(aminoethyl methacrylate) (PAEM) block. The average degree of polymerization (DP) of the PAEM block was varied among 19, 39, and 75, with nearly uniform distribution. With increasing PAEM chain-length, polyplexes formed by the diblock copolymers and plasmid DNA had smaller average particle size and showed higher stability against electrostatic destabilization by salt and heparin. The polymers were not toxic to mouse dendritic cells (DCs) and only displayed chain-length-dependent toxicity at a high concentration (1mg/mL). In vitro gene transfection efficiency and polyplex uptake in DCs were also found to correlate with chain-length of the PAEM block with the longer polymer chain favoring transfection and cellular uptake. The polyplexes induced a modest up-regulation of surface markers for DC maturation that was not significantly dependent on PAEM chain-length. Finally, the polyplex prepared from the longest PAEM block (DP of 75) achieved an average of 20% enhancement over non-condensed anionic dextran in terms of uptake by DCs in the draining lymph nodes 24h after subcutaneous injection into mice. Insights gained from studying such structurally well-defined polymer carriers and their interaction with dendritic cells may contribute to improved design of practically useful DNA vaccine delivery systems. Copyright 2009 Elsevier B.V. All rights reserved.

Monte Carlo simulations of lattice models for single polymer systems

NASA Astrophysics Data System (ADS)

Hsu, Hsiao-Ping

2014-10-01

Single linear polymer chains in dilute solutions under good solvent conditions are studied by Monte Carlo simulations with the pruned-enriched Rosenbluth method up to the chain length N ˜ O(10^4). Based on the standard simple cubic lattice model (SCLM) with fixed bond length and the bond fluctuation model (BFM) with bond lengths in a range between 2 and sqrt{10}, we investigate the conformations of polymer chains described by self-avoiding walks on the simple cubic lattice, and by random walks and non-reversible random walks in the absence of excluded volume interactions. In addition to flexible chains, we also extend our study to semiflexible chains for different stiffness controlled by a bending potential. The persistence lengths of chains extracted from the orientational correlations are estimated for all cases. We show that chains based on the BFM are more flexible than those based on the SCLM for a fixed bending energy. The microscopic differences between these two lattice models are discussed and the theoretical predictions of scaling laws given in the literature are checked and verified. Our simulations clarify that a different mapping ratio between the coarse-grained models and the atomistically realistic description of polymers is required in a coarse-graining approach due to the different crossovers to the asymptotic behavior.

The effect of extended polymer chains on the properties of transparent multi-walled carbon nanotubes/poly(methyl methacrylate/acrylic acid) film

NASA Astrophysics Data System (ADS)

Huang, Yuan-Li; Tien, Hsi-Wen; Ma, Chen-Chi M.; Yu, Yi-Hsiuan; Yang, Shin-Yi; Wei, Ming-Hsiung; Wu, Sheng-Yen

2010-05-01

Optically transparent and electrically conductive thin films composed of multi-walled carbon nanotube (MWCNT) reinforced polymethyl methacrylate/acrylic acid (PMMA/AA) were fabricated using a wire coating technique. Poly(acrylic acid) controls the level of MWCNT dispersion in aqueous mixtures and retains the well-dispersed state in the polymer matrix after solidification resulting from extended polymer chains by adjusting the pH value. The exfoliating the MWCNT bundles by extended polymer chains results in the excellent dispersion of MWCNT. It causes a lower surface electrical resistance at the same MWCNT content. The hydrophilic functional groups (-COO - NA + ) also caused a decrease in the crystallization of PMMA and led to an increase in the transmittance.

The effect of extended polymer chains on the properties of transparent multi-walled carbon nanotubes/poly(methyl methacrylate/acrylic acid) film.

PubMed

Huang, Yuan-Li; Tien, Hsi-Wen; Ma, Chen-Chi M; Yu, Yi-Hsiuan; Yang, Shin-Yi; Wei, Ming-Hsiung; Wu, Sheng-Yen

2010-05-07

Optically transparent and electrically conductive thin films composed of multi-walled carbon nanotube (MWCNT) reinforced polymethyl methacrylate/acrylic acid (PMMA/AA) were fabricated using a wire coating technique. Poly(acrylic acid) controls the level of MWCNT dispersion in aqueous mixtures and retains the well-dispersed state in the polymer matrix after solidification resulting from extended polymer chains by adjusting the pH value. The exfoliating the MWCNT bundles by extended polymer chains results in the excellent dispersion of MWCNT. It causes a lower surface electrical resistance at the same MWCNT content. The hydrophilic functional groups (-COO( - )NA( + )) also caused a decrease in the crystallization of PMMA and led to an increase in the transmittance.

Langmuir-Blodgett Films of Aromatic Schiff’s Bases Functionalized in the Side Chains of Polymethacrylate

DTIC Science & Technology

1991-05-03

Report No. 21 - Latigmuir-Blodgett Films of Aromatic Schiffs Bases , K Fuctionalized in the Side Chains of Polymethacrylate by T. Takahashi, P. Miller...aromatic Schiff’s bases functionalized in the side chains of Polymethacrylate T. Takahashi**, P. Miller*, Y. M. Chen*, L. Samuelson***, D. Galotti, B...has been investigated for polymers in which nonlinear optical (NLO) moieties are attachcd i, the side chain of polymethacrylate (PMA) backbone. Polymer

Phase stability and dynamics of entangled polymer-nanoparticle composites

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mangal, Rahul; Srivastava, Samanvaya; Archer, Lynden A.

Nanoparticle–polymer composites, or polymer–nanoparticle composites (PNCs), exhibit unusual mechanical and dynamical features when the particle size approaches the random coil dimensions of the host polymer. Here, we harness favourable enthalpic interactions between particle-tethered and free, host polymer chains to create model PNCs, in which spherical nanoparticles are uniformly dispersed in high molecular weight entangled polymers. Investigation of the mechanical properties of these model PNCs reveals that the nanoparticles have profound effects on the host polymer motions on all timescales. On short timescales, nanoparticles slow-down local dynamics of the host polymer segments and lower the glass transition temperature. On intermediate timescales,more » where polymer chain motion is typically constrained by entanglements with surrounding molecules, nanoparticles provide additional constraints, which lead to an early onset of entangled polymer dynamics. Finally, on long timescales, nanoparticles produce an apparent speeding up of relaxation of their polymer host.« less

Sequence-Controlled Polymerization on Facially Amphiphilic Templates at Interfaces

DTIC Science & Technology

2016-06-14

controlled chain growth polymerization. We will synthesize a ?- conjugated “parent” polymer by iterative exponential growth (IEG), attach cyclic olefin...template that is programmed to direct sequence- controlled chain growth polymerization. We will synthesize a ?- conjugated “parent” polymer by iterative...polymerization. We will synthesize a π- conjugated “parent” polymer by organometallic iterative exponential growth (IEG),2 attach cyclic olefin “daughter

Surface-induced effects in fluctuation-based measurements of single-polymer elasticity: A direct probe of the radius of gyration

NASA Astrophysics Data System (ADS)

Innes-Gold, Sarah N.; Morgan, Ian L.; Saleh, Omar A.

2018-03-01

Single-molecule measurements of polymer elasticity are powerful, direct probes of both biomolecular structure and principles of polymer physics. Recent work has revealed low-force regimes in which biopolymer elasticity is understood through blob-based scaling models. However, the small tensions required to observe these regimes have the potential to create measurement biases, particularly due to the increased interactions of the polymer chain with tethering surfaces. Here, we examine one experimentally observed bias, in which fluctuation-based estimates of elasticity report an unexpectedly low chain compliance. We show that the effect is in good agreement with predictions based on quantifying the exclusion effect of the surface through an image-method calculation of available polymer configurations. The analysis indicates that the effect occurs at an external tension inversely proportional to the polymer's zero-tension radius of gyration. We exploit this to demonstrate a self-consistent scheme for estimating the radius of gyration of the tethered polymer. This is shown in measurements of both hyaluronic acid and poly(ethylene glycol) chains.

Swelling of biological and semiflexible polyelectrolytes.

PubMed

Dobrynin, Andrey V; Carrillo, Jan-Michael Y

2009-10-21

We have developed a theoretical model of swelling of semiflexible (biological) polyelectrolytes in salt solutions. Our approach is based on separation of length scales which allowed us to split a chain's electrostatic energy into two parts that describe local and remote electrostatic interactions along the polymer backbone. The local part takes into account interactions between charged monomers that are separated by distances along the polymer backbone shorter than the chain's persistence length. These electrostatic interactions renormalize chain persistence length. The second part includes electrostatic interactions between remote charged pairs along the polymer backbone located at distances larger than the chain persistence length. These interactions are responsible for chain swelling. In the framework of this approach we calculated effective chain persistence length and chain size as a function of the Debye screening length, chain degree of ionization, bare persistence length and chain degree of polymerization. Our crossover expression for the effective chain's persistence length is in good quantitative agreement with the experimental data on DNA. We have been able to fit experimental datasets by using two adjustable parameters: DNA ionization degree (α = 0.15-0.17) and a bare persistence length (l(p) = 40-44 nm).

From Comb-like Polymers to Bottle-Brushes

NASA Astrophysics Data System (ADS)

Liang, Heyi; Cao, Zhen; Dobrynin, Andrey; Sheiko, Sergei

We use a combination of the coarse-grained molecular dynamics simulations and scaling analysis to study conformations of bottle-brushes and comb-like polymers in a melt. Our analysis show that bottle-brushes and comb-like polymers can be in four different conformation regimes depending on the number of monomers between grafted side chains and side chain degree of polymerization. In loosely-grafted comb regime (LC) the degree of polymerization between side chains is longer than side chain degree of polymerization, such that the side chains belonging to the same macromolecule do not overlap. Crossover to a new densely-grafted comb regime (DC) takes place when side chains begin to overlap reducing interpenetration of side chains belonging to different macromolecules. In these two regimes both side-chains and backbone behave as unperturbed linear chains with the effective Kuhn length of the backbone being close to that of linear chain. Further decrease spacer degree of polymerization results in crossover to loosely-grafted bottle-brush regime (LB). In this regime, the bottle-brush backbone is stretched while the side-chains still maintain ideal chain conformation. Finally, for even shorter spacer between grafted side chains, which corresponds to densely-grafted bottle-brush regime (DB), the backbone adopts a fully extended chain conformation, and side-chains begin to stretch to maintain a constant monomer density. NSF DMR-1409710, DMR-1407645, DMR-1624569, DMR-1436201.

Dissolution of covalent adaptable network polymers in organic solvent

NASA Astrophysics Data System (ADS)

Yu, Kai; Yang, Hua; Dao, Binh H.; Shi, Qian; Yakacki, Christopher M.

2017-12-01

It was recently reported that thermosetting polymers can be fully dissolved in a proper organic solvent utilizing a bond-exchange reaction (BER), where small molecules diffuse into the polymer, break the long polymer chains into short segments, and eventually dissolve the network when sufficient solvent is provided. The solvent-assisted dissolution approach was applied to fully recycle thermosets and their fiber composites. This paper presents the first multi-scale modeling framework to predict the dissolution kinetics and mechanics of thermosets in organic solvent. The model connects the micro-scale network dynamics with macro-scale material properties: in the micro-scale, a model is developed based on the kinetics of BERs to describe the cleavage rate of polymer chains and evolution of chain segment length during the dissolution. The micro-scale model is then fed into a continuum-level model with considerations of the transportation of solvent molecules and chain segments in the system. The model shows good prediction on conversion rate of functional groups, degradation of network mechanical properties, and dissolution rate of thermosets during the dissolution. It identifies the underlying kinetic factors governing the dissolution process, and reveals the influence of different material and processing variables on the dissolution process, such as time, temperature, catalyst concentration, and chain length between cross-links.

Adsorption of flexible polymer chains on a surface: Effects of different solvent conditions

NASA Astrophysics Data System (ADS)

Martins, P. H. L.; Plascak, J. A.; Bachmann, M.

2018-05-01

Polymer chains undergoing a continuous adsorption-desorption transition are studied through extensive computer simulations. A three-dimensional self-avoiding walk lattice model of a polymer chain grafted onto a surface has been treated for different solvent conditions. We have used an advanced contact-density chain-growth algorithm, in which the density of contacts can be directly obtained. From this quantity, the order parameter and its fourth-order Binder cumulant are computed, as well as the corresponding critical exponents and the adsorption-desorption transition temperature. As the number of configurations with a given number of surface contacts and monomer-monomer contacts is independent of the temperature and solvent conditions, it can be easily applied to get results for different solvent parameter values without the need of any extra simulations. In analogy to continuous magnetic phase transitions, finite-size-scaling methods have been employed. Quite good results for the critical properties and phase diagram of very long single polymer chains have been obtained by properly taking into account the effects of corrections to scaling. The study covers all solvent effects, going from the limit of super-self-avoiding walks, characterized by effective monomer-monomer repulsion, to poor solvent conditions that enable the formation of compact polymer structures.

Softening of the stiffness of bottle-brush polymers by mutual interaction

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bolisetty, S.; Airaud, C.; Rosenfeldt, S.

2007-04-15

We study bottle-brush macromolecules in a good solvent by small-angle neutron scattering (SANS), static light scattering (SLS), and dynamic light scattering (DLS). These polymers consist of a linear backbone to which long side chains are chemically grafted. The backbone contains about 1600 monomer units (weight average) and every second monomer unit carries side chains with approximately 60 monomer units. The SLS and SANS data extrapolated to infinite dilution lead to the form factor of the polymer that can be described in terms of a wormlike chain with a contour length of 380 nm and a persistence length of 17.5 nm.more » An analysis of the DLS data confirms these model parameters. The scattering intensities taken at finite concentration can be modeled using the polymer reference interaction site model. It reveals a softening of the bottle-brush polymers caused by their mutual interaction. We demonstrate that the persistence decreases from 17.5 nm down to 5 nm upon increasing the concentration from dilute solution to the highest concentration (40.59 g/l) under consideration. The observed softening of the chains is comparable to the theoretically predicted decrease of the electrostatic persistence length of linear polyelectrolyte chains at finite concentrations.« less

Symmetry Breaking in Side Chains Leading to Mixed Orientations and Improved Charge Transport in Isoindigo-alt-Bithiophene Based Polymer Thin Films.

PubMed

Xue, Guobiao; Zhao, Xikang; Qu, Ge; Xu, Tianbai; Gumyusenge, Aristide; Zhang, Zhuorui; Zhao, Yan; Diao, Ying; Li, Hanying; Mei, Jianguo

2017-08-02

The selection of side chains is important in design of conjugated polymers. It not only affects their intrinsic physical properties, but also has an impact on thin film morphologies. Recent reports suggested that a face-on/edge-on bimodal orientation observed in polymer thin films may be responsible for a three-dimensional (3D) charge transport and leads to dramatically improved mobility in donor-acceptor based conjugated polymers. To achieve a bimodal orientation in thin films has been seldom explored from the aspect of molecular design. Here, we demonstrate a design strategy involving the use of asymmetric side chains that enables an isoindigo-based polymer to adopt a distinct bimodal orientation, confirmed by the grazing incidence X-ray diffraction. As a result, the polymer presents an average high mobility of 3.8 ± 0.7 cm 2 V -1 s -1 with a maximum value of 5.1 cm 2 V -1 s -1 , in comparison with 0.47 and 0.51 cm 2 V -1 s -1 obtained from the two reference polymers. This study exemplifies a new strategy to develop the next generation polymers through understanding the property-structure relationship.

Nanostructures and nanosecond dynamics at the polymer/filler interface

NASA Astrophysics Data System (ADS)

Koga, Tad; Barkley, Deborah; Endoh, Maya; Masui, Tomomi; Kishimoto, Hiroyuki; Nagao, Michihiro; Taniguchi, Takashi

We report in-situ nanostructures and nanosecond dynamics of polybutadiene (PB) chains bound to carbon black (CB) fillers (the so-called ``bound polymer layer (BPL)'') in polymer solutions (from dilute to concentrated solutions). The BPL on the CB fillers were extracted by solvent leaching of a CB-filled PB compound and subsequently dispersed in deuterated toluene (a good solvent) to label the BPL for ``contrast-matching'' small-angle neutron scattering (SANS) and neutron spin echo (NSE) techniques. The SANS results demonstrate that the BPL is composed of two regions regardless of molecular weights of PB: the inner unswollen region of 0.5 nm thick and outer swollen region where the polymer chains display a parabolic profile with a diffuse tail. In addition, the NSE results show that the dynamics of the swollen bound chains in the polymer solutions can be explained by the collective dynamics, the so-called ``breathing mode''. Intriguingly, it was also indicative that the collective dynamics is independent of the polymer concentrations and is much faster than that predicted from the solution viscosity. We will discuss the mechanism at the bound polymer-free polymer interface at the nanometer scale. T.K. acknowledges the financial support from NSF Grant (CMMI-1332499).

Structure and Dynamics of Polymer/Polymer grafted nanoparticle composite

NASA Astrophysics Data System (ADS)

Archer, Lynden

Addition of nanoparticles to polymers is a well-practiced methodology for augmenting various properties of the polymer host, including mechanical strength, thermal stability, barrier properties, dimensional stability and wear resistance. Many of these property changes are known to arise from nanoparticle-induced modification of polymer structure and chain dynamics, which are strong functions of the dispersion state of the nanoparticles' and on their relative size (D) to polymer chain dimensions (e.g. Random coil radius Rg or entanglement mesh size a) . This talk will discuss polymer nanocomposites (PNCs) comprised of Polyethylene Glycol (PEG) tethered silica nanoparticles (SiO2-PEG) dispersed in polymers as model systems for investigating phase stability and dynamics of PNCs. On the basis of small-angle X-ray Scattering, it will be shown that favorable enthalpic interactions between particle-tethered chains and a polymer host provides an important mechanism for creating PNCs in which particle aggregation is avoided. The talk will report on polymer and particle scale dynamics in these materials and will show that grafted nanoparticles well dispersed in a polymer host strongly influence the host polymer relaxation dynamics on all timescales and the polymers in turn produce dramatic changes in the nature (from diffusive to hyperdiffusive) and speed of nano particle decorrelation dynamics at the polymer entanglement threshold. A local viscosity model capable of explaining these observations is discussed and the results compared with scaling theories for NP motions in polymers This material is based on work supported by the National Science Foundation Award Nos. DMR-1609125 and CBET-1512297.

Polymer chain collapse induced by many-body dipole correlations.

PubMed

Budkov, Yu A; Kalikin, N N; Kolesnikov, A L

2017-04-01

We present a simple analytical theory of a flexible polymer chain dissolved in a good solvent, carrying permanent freely oriented dipoles on the monomers. We take into account the dipole correlations within the random phase approximation (RPA), as well as a dielectric heterogeneity in the internal polymer volume relative to the bulk solution. We demonstrate that the dipole correlations of monomers can be taken into account as pairwise ones only when the polymer chain is in a coil conformation. In this case the dipole correlations manifest themselves through the Keesom interactions of the permanent dipoles. On the other hand, the dielectric heterogeneity effect (dielectric mismatch effect) leads to the effective interaction between the monomers of the polymeric coil. Both of these effects can be taken into account by renormalizing the second virial coefficient of the monomer-monomer volume interactions. We establish that in the case when the solvent dielectric permittivity exceeds the dielectric permittivity of the polymeric material, the dielectric mismatch effect competes with the dipole attractive interactions, leading to polymer coil expansion. In the opposite case, both the dielectric mismatch effect and the dipole attractive interaction lead to the polymer coil collapse. We analyse the coil-globule transition caused by the dipole correlations of monomers within the many-body theory. We demonstrate that accounting for the dipole correlations higher than the pairwise ones smooths this pure electrostatics driven coil-globule transition of the polymer chain.

Snap-through instability analysis of dielectric elastomers with consideration of chain entanglements

NASA Astrophysics Data System (ADS)

Zhu, Jiakun; Luo, Jun; Xiao, Zhongmin

2018-06-01

It is widely recognized that the extension limit of polymer chains has a significant effect on the snap-through instability of dielectric elastomers (DEs). The snap-through instability performance of DEs has been extensively studied by two limited-stretch models, i.e., the eight-chain model and Gent model. However, the real polymer networks usually have many entanglements due to the impenetrability of the network chains as well as a finite extensibility resulting from the full stretching of the polymer chains. The effects of entanglements on the snap-through instability of DEs cannot be captured by the previous two limited-stretch models. In this paper, the nonaffine model proposed by Davidson and Goulbourne is adopted to characterize the influence of entanglements and extension limit of the polymer chains. It is demonstrated that the nonaffine model is almost identical to the eight-chain model and is close to the Gent model if we ignore the effects of chain entanglements and adopt the affine assumption. The suitability of the nonaffine model to characterize the mechanical behavior of elastomers is validated by fitting the experimental results reported in the open literature. After that, the snap-through stability performance of an ideal DE membrane under equal-biaxial prestretches is studied with the nonaffine model. It is revealed that besides the prestretch and chain extension limit, the chain entanglements can markedly influence the snap-through instability and the path to failure of DEs. These results provide a more comprehensive understanding on the snap-through instability of a DE and may be helpful to guide the design of DE devices.

Structure and dynamics of solvated polyethylenimine chains

NASA Astrophysics Data System (ADS)

Beu, Titus A.; Farcaş, Alexandra

2017-12-01

Polimeric gene-delivery carriers have attracted great interest in recent years, owing to their applicability in gene therapy. In particular, cationic polymers represent the most promising delivery vectors for nucleic acids into the cells. This study presents extensive atomistic molecular dynamics simulations of linear polyethylenimine chains. The simulations show that the variation of the chain size and protonation fraction causes a substantial change of the diffusion coefficient. Examination of the solvated chains suggests the possibility of controlling the polymer diffusion mobility in solution.

Structure and Dynamics of Solvated Polymers near a Silica Surface: On the Different Roles Played by Solvent.

PubMed

Perrin, Elsa; Schoen, Martin; Coudert, François-Xavier; Boutin, Anne

2018-04-26

Whereas it is experimentally known that the inclusion of nanoparticles in hydrogels can lead to a mechanical reinforcement, a detailed molecular understanding of the adhesion mechanism is still lacking. Here we use coarse-grained molecular dynamics simulations to investigate the nature of the interface between silica surfaces and solvated polymers. We show how differences in the nature of the polymer and the polymer-solvent interactions can lead to drastically different behavior of the polymer-surface adhesion. Comparing explicit and implicit solvent models, we conclude that this effect cannot be fully described in an implicit solvent. We highlight the crucial role of polymer solvation for the adsorption of the polymer chain on the silica surface, the significant dynamics of polymer chains on the surface, and details of the modifications in the structure solvated polymer close to the interface.

Polymers for metal extractions in carbon dioxide

DOEpatents

DeSimone, Joseph M.; Tumas, William; Powell, Kimberly R.; McCleskey, T. Mark; Romack, Timothy J.; McClain, James B.; Birnbaum, Eva R.

2001-01-01

A composition useful for the extraction of metals and metalloids comprises (a) carbon dioxide fluid (preferably liquid or supercritical carbon dioxide); and (b) a polymer in the carbon dioxide, the polymer having bound thereto a ligand that binds the metal or metalloid; with the ligand bound to the polymer at a plurality of locations along the chain length thereof (i.e., a plurality of ligands are bound at a plurality of locations along the chain length of the polymer). The polymer is preferably a copolymer, and the polymer is preferably a fluoropolymer such as a fluoroacrylate polymer. The extraction method comprises the steps of contacting a first composition containing a metal or metalloid to be extracted with a second composition, the second composition being as described above; and then extracting the metal or metalloid from the first composition into the second composition.

Formalism for calculation of polymer-solvent-mediated potential

NASA Astrophysics Data System (ADS)

Zhou, Shiqi

2006-07-01

A simple theoretical approach is proposed for calculation of a solvent-mediated potential (SMP) between two colloid particles immersed in a polymer solvent bath in which the polymer is modeled as a chain with intramolecular degrees of freedom. The present recipe is only concerned with the estimation of the density profile of a polymer site around a single solute colloid particle instead of two solute colloid particles separated by a varying distance as done in existing calculational methods for polymer-SMP. Therefore the present recipe is far simpler for numerical implementation than the existing methods. The resultant predictions for the polymer-SMP and polymer solvent-mediated mean force (polymer-SMMF) are in very good agreement with available simulation data. With the present recipe, change tendencies of the contact value and second virial coefficiency of the SMP as a function of size ratio between the colloid particle and polymer site, the number of sites per chain, and the polymer concentration are investigated in detail. The metastable critical polymer concentration as a function of size ratio and the number of sites per chain is also reported for the first time. To yield the numerical solution of the present recipe at less than 1min on a personal computer, a rapid and accurate algorithm for the numerical solution of the classical density functional theory is proposed to supply rapid and accurate estimation of the density profile of the polymer site as an input into the present formalism.

Polymerase chain reaction system using magnetic beads for analyzing a sample that includes nucleic acid

DOE Office of Scientific and Technical Information (OSTI.GOV)

Nasarabadi, Shanavaz

2011-01-11

A polymerase chain reaction system for analyzing a sample containing nucleic acid includes providing magnetic beads; providing a flow channel having a polymerase chain reaction chamber, a pre polymerase chain reaction magnet position adjacent the polymerase chain reaction chamber, and a post pre polymerase magnet position adjacent the polymerase chain reaction chamber. The nucleic acid is bound to the magnetic beads. The magnetic beads with the nucleic acid flow to the pre polymerase chain reaction magnet position in the flow channel. The magnetic beads and the nucleic acid are washed with ethanol. The nucleic acid in the polymerase chain reactionmore » chamber is amplified. The magnetic beads and the nucleic acid are separated into a waste stream containing the magnetic beads and a post polymerase chain reaction mix containing the nucleic acid. The reaction mix containing the nucleic acid flows to an analysis unit in the channel for analysis.« less

Polymer models of interphase chromosomes

PubMed Central

Vasquez, Paula A; Bloom, Kerry

2014-01-01

Clear organizational patterns on the genome have emerged from the statistics of population studies of fixed cells. However, how these results translate into the dynamics of individual living cells remains unexplored. We use statistical mechanics models derived from polymer physics to inquire into the effects that chromosome properties and dynamics have in the temporal and spatial behavior of the genome. Overall, changes in the properties of individual chains affect the behavior of all other chains in the domain. We explore two modifications of chain behavior: single chain motion and chain-chain interactions. We show that there is not a direct relation between these effects, as increase in motion, doesn’t necessarily translate into an increase on chain interaction. PMID:25482191

Brownian dynamics simulations of a flexible polymer chain which includes continuous resistance and multibody hydrodynamic interactions

NASA Astrophysics Data System (ADS)

Butler, Jason E.; Shaqfeh, Eric S. G.

2005-01-01

Using methods adapted from the simulation of suspension dynamics, we have developed a Brownian dynamics algorithm with multibody hydrodynamic interactions for simulating the dynamics of polymer molecules. The polymer molecule is modeled as a chain composed of a series of inextensible, rigid rods with constraints at each joint to ensure continuity of the chain. The linear and rotational velocities of each segment of the polymer chain are described by the slender-body theory of Batchelor [J. Fluid Mech. 44, 419 (1970)]. To include hydrodynamic interactions between the segments of the chain, the line distribution of forces on each segment is approximated by making a Legendre polynomial expansion of the disturbance velocity on the segment, where the first two terms of the expansion are retained in the calculation. Thus, the resulting linear force distribution is specified by a center of mass force, couple, and stresslet on each segment. This method for calculating the hydrodynamic interactions has been successfully used to simulate the dynamics of noncolloidal suspensions of rigid fibers [O. G. Harlen, R. R. Sundararajakumar, and D. L. Koch, J. Fluid Mech. 388, 355 (1999); J. E. Butler and E. S. G. Shaqfeh, J. Fluid Mech. 468, 204 (2002)]. The longest relaxation time and center of mass diffusivity are among the quantities calculated with the simulation technique. Comparisons are made for different levels of approximation of the hydrodynamic interactions, including multibody interactions, two-body interactions, and the "freely draining" case with no interactions. For the short polymer chains studied in this paper, the results indicate a difference in the apparent scaling of diffusivity with polymer length for the multibody versus two-body level of approximation for the hydrodynamic interactions.

Brownian dynamics simulations of a flexible polymer chain which includes continuous resistance and multibody hydrodynamic interactions.

PubMed

Butler, Jason E; Shaqfeh, Eric S G

2005-01-01

Using methods adapted from the simulation of suspension dynamics, we have developed a Brownian dynamics algorithm with multibody hydrodynamic interactions for simulating the dynamics of polymer molecules. The polymer molecule is modeled as a chain composed of a series of inextensible, rigid rods with constraints at each joint to ensure continuity of the chain. The linear and rotational velocities of each segment of the polymer chain are described by the slender-body theory of Batchelor [J. Fluid Mech. 44, 419 (1970)]. To include hydrodynamic interactions between the segments of the chain, the line distribution of forces on each segment is approximated by making a Legendre polynomial expansion of the disturbance velocity on the segment, where the first two terms of the expansion are retained in the calculation. Thus, the resulting linear force distribution is specified by a center of mass force, couple, and stresslet on each segment. This method for calculating the hydrodynamic interactions has been successfully used to simulate the dynamics of noncolloidal suspensions of rigid fibers [O. G. Harlen, R. R. Sundararajakumar, and D. L. Koch, J. Fluid Mech. 388, 355 (1999); J. E. Butler and E. S. G. Shaqfeh, J. Fluid Mech. 468, 204 (2002)]. The longest relaxation time and center of mass diffusivity are among the quantities calculated with the simulation technique. Comparisons are made for different levels of approximation of the hydrodynamic interactions, including multibody interactions, two-body interactions, and the "freely draining" case with no interactions. For the short polymer chains studied in this paper, the results indicate a difference in the apparent scaling of diffusivity with polymer length for the multibody versus two-body level of approximation for the hydrodynamic interactions. (c) 2005 American Institute of Physics.

Healing of polymer interfaces: Interfacial dynamics, entanglements, and strength

NASA Astrophysics Data System (ADS)

Ge, Ting; Robbins, Mark O.; Perahia, Dvora; Grest, Gary S.

2014-07-01

Self-healing of polymer films often takes place as the molecules diffuse across a damaged region, above their melting temperature. Using molecular dynamics simulations we probe the healing of polymer films and compare the results with those obtained for thermal welding of homopolymer slabs. These two processes differ from each other in their interfacial structure since damage leads to increased polydispersity and more short chains. A polymer sample was cut into two separate films that were then held together in the melt state. The recovery of the damaged film was followed as time elapsed and polymer molecules diffused across the interface. The mass uptake and formation of entanglements, as obtained from primitive path analysis, are extracted and correlated with the interfacial strength obtained from shear simulations. We find that the diffusion across the interface is significantly faster in the damaged film compared to welding because of the presence of short chains. Though interfacial entanglements increase more rapidly for the damaged films, a large fraction of these entanglements are near chain ends. As a result, the interfacial strength of the healing film increases more slowly than for welding. For both healing and welding, the interfacial strength saturates as the bulk entanglement density is recovered across the interface. However, the saturation strength of the damaged film is below the bulk strength for the polymer sample. At saturation, cut chains remain near the healing interface. They are less entangled and as a result they mechanically weaken the interface. Chain stiffness increases the density of entanglements, which increases the strength of the interface. Our results show that a few entanglements across the interface are sufficient to resist interfacial chain pullout and enhance the mechanical strength.

Triazine-based sequence-defined polymers with side-chain diversity and backbone-backbone interaction motifs

DOE PAGES

Grate, Jay W.; Mo, Kai -For; Daily, Michael D.

2016-02-10

Sequence control in polymers, well-known in nature, encodes structure and functionality. Here we introduce a new architecture, based on the nucleophilic aromatic substitution chemistry of cyanuric chloride, that creates a new class of sequence-defined polymers dubbed TZPs. Proof of concept is demonstrated with two synthesized hexamers, having neutral and ionizable side chains. Molecular dynamics simulations show backbone–backbone interactions, including H-bonding motifs and pi–pi interactions. This architecture is arguably biomimetic while differing from sequence-defined polymers having peptide bonds. In conclusion, the synthetic methodology supports the structural diversity of side chains known in peptides, as well as backbone–backbone hydrogen-bonding motifs, and willmore » thus enable new macromolecules and materials with useful functions.« less

Triazine-Based Sequence-Defined Polymers with Side-Chain Diversity and Backbone-Backbone Interaction Motifs.

PubMed

Grate, Jay W; Mo, Kai-For; Daily, Michael D

2016-03-14

Sequence control in polymers, well-known in nature, encodes structure and functionality. Here we introduce a new architecture, based on the nucleophilic aromatic substitution chemistry of cyanuric chloride, that creates a new class of sequence-defined polymers dubbed TZPs. Proof of concept is demonstrated with two synthesized hexamers, having neutral and ionizable side chains. Molecular dynamics simulations show backbone-backbone interactions, including H-bonding motifs and pi-pi interactions. This architecture is arguably biomimetic while differing from sequence-defined polymers having peptide bonds. The synthetic methodology supports the structural diversity of side chains known in peptides, as well as backbone-backbone hydrogen-bonding motifs, and will thus enable new macromolecules and materials with useful functions. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Triazine-based sequence-defined polymers with side-chain diversity and backbone-backbone interaction motifs

DOE Office of Scientific and Technical Information (OSTI.GOV)

Grate, Jay W.; Mo, Kai -For; Daily, Michael D.

Sequence control in polymers, well-known in nature, encodes structure and functionality. Here we introduce a new architecture, based on the nucleophilic aromatic substitution chemistry of cyanuric chloride, that creates a new class of sequence-defined polymers dubbed TZPs. Proof of concept is demonstrated with two synthesized hexamers, having neutral and ionizable side chains. Molecular dynamics simulations show backbone–backbone interactions, including H-bonding motifs and pi–pi interactions. This architecture is arguably biomimetic while differing from sequence-defined polymers having peptide bonds. In conclusion, the synthetic methodology supports the structural diversity of side chains known in peptides, as well as backbone–backbone hydrogen-bonding motifs, and willmore » thus enable new macromolecules and materials with useful functions.« less

Main chain acid-degradable polymers for the delivery of bioactive materials

DOEpatents

Frechet, Jean M. J. [Oakland, CA; Standley, Stephany M [Evanston, IL; Jain, Rachna [Milpitas, CA; Lee, Cameron C [Cambridge, MA

2012-03-20

Novel main chain acid degradable polymer backbones and drug delivery systems comprised of materials capable of delivering bioactive materials to cells for use as vaccines or other therapeutic agents are described. The polymers are synthesized using monomers that contain acid-degradable linkages cleavable under mild acidic conditions. The main chain of the resulting polymers readily degrade into many small molecules at low pH, but remain relatively stable and intact at physiological pH. The new materials have the common characteristic of being able to degrade by acid hydrolysis under conditions commonly found within the endosomal or lysosomal compartments of cells thereby releasing their payload within the cell. The materials can also be used for the delivery of therapeutics to the acidic regions of tumors and other sites of inflammation.

Developing new methods for the mono-end functionalization of living ring opening metathesis polymers.

PubMed

Kilbinger, Andreas F M

2012-01-01

In this article we present a review of our recent results in one area of research we are involved in. All research efforts in our group focus on functional polymers and new ways of gaining higher levels of control with regard to the placement of functional groups within these polymers. Here, the living ring opening metathesis polymerization (ROMP) will be reviewed for which end-functionalization methods had been rare until very recently. Polymers carrying particular functional groups only at the chain-ends are, however, very interesting for a variety of industrial and academic applications. Polymeric surfactants and polymer-protein conjugates are two examples for the former and polymer-β-sheet-peptide conjugates one example for the latter. The functionalization of macroscopic or nanoscopic surfaces often relies on mono-end functional polymers. Complex macromolecular architectures are often constructed from macromolecules carrying exactly one functional group at their chain- end. The ring opening metathesis polymerization is particularly interesting in this context as it is one of the most functional group tolerant polymerization methods known. Additionally, high molecular weight polymers are readily accessible with this technique, a feature that living radical polymerizations often struggle to achieve. Finding new ways of functionalizing the polymer chain-end of ROMP polymers has therefore been a task long overdue. Here, we present our contribution to this area of research.

Deuteration as a Means to Tune Crystallinity of Conducting Polymers

DOE PAGES

Jakowski, Jacek; Huang, Jingsong; Garashchuk, Sophya; ...

2017-08-25

The effects of deuterium isotope substitution on conjugated polymer chain stacking of poly(3-hexylthiophene) is studied in this paper experimentally by X-ray diffraction (XRD) in combination with gel permeation chromatography and theoretically using density functional theory and quantum molecular dynamics. For four P3HT materials with different levels of deuteration (pristine, main-chain deuterated, side-chain deuterated, and fully deuterated), the XRD measurements show that main-chain thiophene deuteration significantly reduces crystallinity, regardless of the side-chain deuteration. The reduction of crystallinity due to the main-chain deuteration is a quantum nuclear effect resulting from a static zero-point vibrational energy combined with a dynamic correlation of themore » dipole fluctuations. The quantum molecular dynamics simulations confirm the interchain correlation of the proton–proton and deuteron–deuteron motions but not of the proton–deuteron motion. Thus and finally, isotopic purity is an important factor affecting stability and properties of conjugated polymer crystals, which should be considered in the design of electronic and spintronic devices.« less

Deuteration as a Means to Tune Crystallinity of Conducting Polymers

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jakowski, Jacek; Huang, Jingsong; Garashchuk, Sophya

The effects of deuterium isotope substitution on conjugated polymer chain stacking of poly(3-hexylthiophene) is studied in this paper experimentally by X-ray diffraction (XRD) in combination with gel permeation chromatography and theoretically using density functional theory and quantum molecular dynamics. For four P3HT materials with different levels of deuteration (pristine, main-chain deuterated, side-chain deuterated, and fully deuterated), the XRD measurements show that main-chain thiophene deuteration significantly reduces crystallinity, regardless of the side-chain deuteration. The reduction of crystallinity due to the main-chain deuteration is a quantum nuclear effect resulting from a static zero-point vibrational energy combined with a dynamic correlation of themore » dipole fluctuations. The quantum molecular dynamics simulations confirm the interchain correlation of the proton–proton and deuteron–deuteron motions but not of the proton–deuteron motion. Thus and finally, isotopic purity is an important factor affecting stability and properties of conjugated polymer crystals, which should be considered in the design of electronic and spintronic devices.« less

Unlocking Chain Exchange in Highly Amphiphilic Block Polymer Micellar Systems: Influence of Agitation.

PubMed

Murphy, Ryan P; Kelley, Elizabeth G; Rogers, Simon A; Sullivan, Millicent O; Epps, Thomas H

2014-11-18

Chain exchange between block polymer micelles in highly selective solvents, such as water, is well-known to be arrested under quiescent conditions, yet this work demonstrates that simple agitation methods can induce rapid chain exchange in these solvents. Aqueous solutions containing either pure poly(butadiene- b -ethylene oxide) or pure poly(butadiene- b -ethylene oxide- d 4 ) micelles were combined and then subjected to agitation by vortex mixing, concentric cylinder Couette flow, or nitrogen gas sparging. Subsequently, the extent of chain exchange between micelles was quantified using small angle neutron scattering. Rapid vortex mixing induced chain exchange within minutes, as evidenced by a monotonic decrease in scattered intensity, whereas Couette flow and sparging did not lead to measurable chain exchange over the examined time scale of hours. The linear kinetics with respect to agitation time suggested a surface-limited exchange process at the air-water interface. These findings demonstrate the strong influence of processing conditions on block polymer solution assemblies.

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

PubMed

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

2016-09-20

Protein-polymer conjugates are unique constructs that combine the chemical properties of a synthetic polymer chain with the biological properties of a biomacromolecule. This often leads to improved stabilities, solubilities, and in vivo half-lives of the resulting conjugates, and expands the range of applications for the proteins. However, early chemical methods for protein-polymer conjugation often required multiple polymer modifications, which were tedious and low yielding. To solve these issues, work in our laboratory has focused on the development of controlled radical polymerization (CRP) techniques to improve synthesis of protein-polymer conjugates. Initial efforts focused on the one-step syntheses of protein-reactive polymers through the use of functionalized initiators and chain transfer agents. A variety of functional groups such as maleimide and pyridyl disulfide could be installed with high end-group retention, which could then react with protein functional groups through mild and biocompatible chemistries. While this grafting to method represented a significant advance in conjugation technique, purification and steric hindrance between large biomacromolecules and polymer chains often led to low conjugation yields. Therefore, a grafting from approach was developed, wherein a polymer chain is grown from an initiating site on a functionalized protein. These conjugates have demonstrated improved homogeneity, characterization, and easier purification, while maintaining protein activity. Much of this early work utilizing CRP techniques focused on polymers made up of biocompatible but nonfunctional monomer units, often containing oligoethylene glycol meth(acrylate) or N-isopropylacrylamide. These branched polymers have significant advantages compared to the historically used linear poly(ethylene glycols) including decreased viscosities and thermally responsive behavior, respectively. Recently, we were motivated to use CRP techniques to develop polymers with rationally designed and functional biological properties for conjugate preparation. Specifically, two families of saccharide-inspired polymers were developed for stabilization and activation of therapeutic biomolecules. A series of polymers with trehalose side-chains and vinyl backbones were prepared and used to stabilize proteins against heat and lyophilization stress as both conjugates and additives. These materials, which combine properties of osmolytes with nonionic surfactants, have significant potential for in vivo therapeutic use. Additionally, polymers that mimic the structure of the naturally occurring polysaccharide heparin were prepared. These polymers contained negatively charged sulfonate groups and imparted stabilization to a heparin-binding growth factor after conjugation. A screen of other sulfonated polymers led to the development of a polymer with improved heparin mimesis, enhancing both stability and activity of the protein to which it was attached. Chemical improvements over the past decade have enabled the preparation of a diverse set of protein-polymer conjugates by controlled polymerization techniques. Now, the field should thoroughly explore and expand both the range of polymer structures and also the applications available to protein-polymer conjugates. As we move beyond medicine toward broader applications, increased collaboration and interdisciplinary work will result in the further development of this exciting field.

Design and synthesis of digitally encoded polymers that can be decoded and erased

NASA Astrophysics Data System (ADS)

Roy, Raj Kumar; Meszynska, Anna; Laure, Chloé; Charles, Laurence; Verchin, Claire; Lutz, Jean-François

2015-05-01

Biopolymers such as DNA store information in their chains using controlled sequences of monomers. Here we describe a non-natural information-containing macromolecule that can store and retrieve digital information. Monodisperse sequence-encoded poly(alkoxyamine amide)s were synthesized using an iterative strategy employing two chemoselective steps: the reaction of a primary amine with an acid anhydride and the radical coupling of a carbon-centred radical with a nitroxide. A binary code was implemented in the polymer chains using three monomers: one nitroxide spacer and two interchangeable anhydrides defined as 0-bit and 1-bit. This methodology allows encryption of any desired sequence in the chains. Moreover, the formed sequences are easy to decode using tandem mass spectrometry. Indeed, these polymers follow predictable fragmentation pathways that can be easily deciphered. Moreover, poly(alkoxyamine amide)s are thermolabile. Thus, the digital information encrypted in the chains can be erased by heating the polymers in the solid state or in solution.

Design and synthesis of digitally encoded polymers that can be decoded and erased.

PubMed

Roy, Raj Kumar; Meszynska, Anna; Laure, Chloé; Charles, Laurence; Verchin, Claire; Lutz, Jean-François

2015-05-26

Biopolymers such as DNA store information in their chains using controlled sequences of monomers. Here we describe a non-natural information-containing macromolecule that can store and retrieve digital information. Monodisperse sequence-encoded poly(alkoxyamine amide)s were synthesized using an iterative strategy employing two chemoselective steps: the reaction of a primary amine with an acid anhydride and the radical coupling of a carbon-centred radical with a nitroxide. A binary code was implemented in the polymer chains using three monomers: one nitroxide spacer and two interchangeable anhydrides defined as 0-bit and 1-bit. This methodology allows encryption of any desired sequence in the chains. Moreover, the formed sequences are easy to decode using tandem mass spectrometry. Indeed, these polymers follow predictable fragmentation pathways that can be easily deciphered. Moreover, poly(alkoxyamine amide)s are thermolabile. Thus, the digital information encrypted in the chains can be erased by heating the polymers in the solid state or in solution.

Microscopic theory of light-induced deformation in amorphous side-chain azobenzene polymers.

PubMed

Toshchevikov, V; Saphiannikova, M; Heinrich, G

2009-04-16

We propose a microscopic theory of light-induced deformation of side-chain azobenzene polymers taking into account the internal structure of polymer chains. Our theory is based on the fact that interaction of chromophores with the polarized light leads to the orientation anisotropy of azobenzene macromolecules which is accompanied by the appearance of mechanical stress. It is the first microscopic theory which provides the value of the light-induced stress larger than the yield stress. This result explains a possibility for the inscription of surface relief gratings in glassy side-chain azobenzene polymers. For some chemical architectures, elongation of a sample demonstrates a nonmonotonic behavior with the light intensity and can change its sign (a stretched sample starts to be uniaxially compressed), in agreement with experiments. Using a viscoplastic approach, we show that the irreversible strain of a sample, which remains after the light is switched off, decreases with increasing temperature and can disappear at certain temperature below the glass transition temperature. This theoretical prediction is also confirmed by recent experiments.

From Semi- to Full-Two-Dimensional Conjugated Side-Chain Design: A Way toward Comprehensive Solar Energy Absorption

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chao, Pengjie; Wang, Huan; Qu, Shiwei

Two polymers with fully two-dimensional (2D) conjugated side chains, 2D-PTB-Th and 2D-PTB-TTh, were synthesized and characterized through simultaneously integrating the 2D-TT and the 2D-BDT monomers onto the polymer backbone. Resulting from the synergistic effect from the conjugated side chains on both monomers, the two polymers showed remarkably efficient absorption of the sunlight and improved pi-pi intermolecular interactions for efficient charge carrier transport. The optimized bulk heterojunction device based on 2D-PTB-Th and PC71BM shows a higher PCE of 9.13% compared to PTB7-Th with a PCE of 8.26%, which corresponds to an approximately 10% improvement in solar energy conversion. The fully 2D-conjugatedmore » side-chain concept reported here developed a new molecular design strategy for polymer materials with enhanced sunlight absorption and efficient solar energy conversion.« less

Polymer absorption in dense polymer brushes vs. polymer adsorption on the brush-solvent interface

NASA Astrophysics Data System (ADS)

Milchev, Andrey; Binder, Kurt

2014-06-01

Molecular-dynamics simulations of a coarse-grained model of a dense brush of flexible polymers (of type A) interacting with a long flexible macromolecule (of type B) are presented, considering the case of an attractive AB interaction, while effective interactions between AA and BB pairs of monomers are repulsive. Varying the strength \\varepsilon_{AB} of the attraction between unlike monomers, an adsorption transition at some critical value \\varepsilon^c_{AB} is found, where the B-chain is bound to the brush-solvent interface, similar to the adsorption on a planar solid substrate. However, when \\varepsilon_{AB} is much higher than \\varepsilon^c_{AB} , the long macromolecule is gradually “sucked in” the brush, developing many pieces that are locally stretched in the z-direction perpendicular to the substrate, in order to fit between the brush chains. The resulting hairpin-like structures of the absorbed chain shows up via oscillatory decay of the bond vector autocorrelation function. Chain relaxation is only possible via reptation.

Protein adsorption to poly(ethylenimine)-modified Sepharose FF: I. a critical ionic capacity for drastically enhanced capacity and uptake kinetics.

PubMed

Yu, Lin-Ling; Tao, Shi-Peng; Dong, Xiao-Yan; Sun, Yan

2013-08-30

To explore the details of protein uptake to polymer-grafted ion exchangers, Sepharose FF was modified with poly(ethylenimine) (PEI) to prepare anion exchanger of 10 different ionic capacities (ICs, 100-1220mmol/L). Adsorption equilibria and kinetics of bovine serum albumin (BSA) were then studied. It is found that ionic capacity, i.e., the coupling density of PEI, had significant effect on both adsorption capacity (qm) and effective protein diffusivity (De). With increasing ionic capacity, the qm value increased rapidly at IC<260mmol/L and then increased slowly till reaching a plateau at IC=600mmol/L. In the IC range of 100-600mmol/L, however, the De values kept at a low level (De/D0<0.07); it first decreased from 0.05±0.01 at IC=100mmol/L to 0.01±0.01 at IC=260mmol/L and then increased to 0.06±0.01 at IC=600mmol/L. Thereafter, sharp increases of the qm and De values [36% (from 201 to 273mg/mL) and 670% (from 0.06±0.01 to 0.49±0.04), respectively] were observed in the narrow range of IC from 600 to 740mmol/L. Finally, at IC>740mmol/L, the qm value decreased significantly while the De value increased moderately with increasing the IC. The results indicate that PEI chains played an important role in protein adsorption and transport. In brief, there was a critical IC (cIC) or PEI chain density, above which protein adsorption and transport behaviors changed drastically. The cIC was identified to be about 600mmol/L. Estimation of PEI grafting-layer thickness suggests that PEI chains formed an extended three-dimensional grafting-layer at IC>cIC, which provided high flexibility as well as accessibility of the chains for protein binding. Therefore, at IC>cIC, the adjacent PEI chains became close and flexible enough, leading to facilitated transport of adsorbed protein molecules by the interactions of neighboring chains mediated by the bound molecules. It is regarded as "chain delivery" effect. At the same time, improved accessibility of binding sites led the significant increase of binding capacity. The decrease of qm value at IC>740mmol/L is considered due to the decrease of effective porosity. The research has thus provided new insight into protein adsorption and transport in polymer-grafted ion-exchange media. Copyright © 2013 Elsevier B.V. All rights reserved.

Topology of polymer chains under nanoscale confinement.

PubMed

Satarifard, Vahid; Heidari, Maziar; Mashaghi, Samaneh; Tans, Sander J; Ejtehadi, Mohammad Reza; Mashaghi, Alireza

2017-08-24

Spatial confinement limits the conformational space accessible to biomolecules but the implications for bimolecular topology are not yet known. Folded linear biopolymers can be seen as molecular circuits formed by intramolecular contacts. The pairwise arrangement of intra-chain contacts can be categorized as parallel, series or cross, and has been identified as a topological property. Using molecular dynamics simulations, we determine the contact order distributions and topological circuits of short semi-flexible linear and ring polymer chains with a persistence length of l p under a spherical confinement of radius R c . At low values of l p /R c , the entropy of the linear chain leads to the formation of independent contacts along the chain and accordingly, increases the fraction of series topology with respect to other topologies. However, at high l p /R c , the fraction of cross and parallel topologies are enhanced in the chain topological circuits with cross becoming predominant. At an intermediate confining regime, we identify a critical value of l p /R c , at which all topological states have equal probability. Confinement thus equalizes the probability of more complex cross and parallel topologies to the level of the more simple, non-cooperative series topology. Moreover, our topology analysis reveals distinct behaviours for ring- and linear polymers under weak confinement; however, we find no difference between ring- and linear polymers under strong confinement. Under weak confinement, ring polymers adopt parallel and series topologies with equal likelihood, while linear polymers show a higher tendency for series arrangement. The radial distribution analysis of the topology reveals a non-uniform effect of confinement on the topology of polymer chains, thereby imposing more pronounced effects on the core region than on the confinement surface. Additionally, our results reveal that over a wide range of confining radii, loops arranged in parallel and cross topologies have nearly the same contact orders. Such degeneracy implies that the kinetics and transition rates between the topological states cannot be solely explained by contact order. We expect these findings to be of general importance in understanding chaperone assisted protein folding, chromosome architecture, and the evolution of molecular folds.

Two new Co(II)-MOFs based on polymeric chain building units: Crystal structures, and magnetic properties

DOE Office of Scientific and Technical Information (OSTI.GOV)

Han, Min-Le; Key Laboratory of Synthetic and Natural Functional Molecule Chemistry of the Ministry of Education, College of Chemistry & Materials Science, Northwest University, Xi’an 710069; Wu, Ya-Pan

2015-10-15

Two new Co(II) metal-organic frameworks, namely [Co{sub 2}(bpm)(H{sub 2}O){sub 3}(L)]{sub n} (1) and ([Co(bpe)(H{sub 2}O)(H{sub 2}L)]·(bpe){sub 0.5}·(H{sub 2}O)){sub n} (2), (H{sub 4}L=1,1′:2′,1″-terphenyl-3,3″,4′,5′-tetracarboxylic acid, bpm=bis(4-pyridyl)amine, bpe=1,2-bis(4-pyridyl)ethene), have been obtained under hydrothermal conditions. Both complexes 1 and 2 have been characterized by elemental analysis, IR spectra, single-crystal X-ray diffraction, powder X-ray diffraction (PXRD), and thermogravimetric analysis (TGA). Complexes 1 and 2 consist of 1D Co(II) chains bridging by carboxylate groups in syn-anti fashion. 1 shows a novel 3D tri-nodal (4,6,10)-connected net with a (3.4{sup 3}.5{sup 2}){sub 2}(3{sup 2}.4{sup 14}.5{sup 12}.6{sup 12}.7{sup 4}.8)(3{sup 2}.4{sup 2}.5{sup 5}.6{sup 4}.7{sup 2}) topology. While 2 exhibits amore » 2D sql layer. Magnetic susceptibility measurements indicate that both 1 and 2 show weak antiferromagnetic interactions between the adjacent Co(II) ions in 300–8 K for 1 and 300–16 K for 2, respectively, and then 2 also displays ferromagnetic coupling at lower temperatures. - Graphical abstract: Two Co(II) coordination polymers with similar metal chain bridging by carboxylates in syn-anti fashion have been synthesized. Both 1 and 2 show weak antiferromagnetic interactions in high temperature, and then 2 also displays ferromagnetic coupling at lower temperatures. - Highlights: • Two Co(II) coordination polymers with similar metal chain bridging by carboxylates. • A novel 3D (4,6,10)-connected net and a 2D sql layers. • A antiferromagnetic coupling at high temperature for 1 and 2. • A ferromagnetic coupling at lower temperature for 2.« less

A series of divalent metal coordination polymers based on isomeric tetracarboxylic acids: synthesis, structures and magnetic properties.

PubMed

Han, Min-Le; Duan, Ya-Ping; Li, Dong-Sheng; Xu, Guo-Wang; Wu, Ya-Pan; Zhao, Jun

2014-12-14

Five new coordination polymers, namely, [Mn(2,2′-bipy)(H2O)2(H2L1)]n (1), {[Co(btb)(H2O)2(H2L1)]·0.5H2O}n (2), [Co(bib)(H2O)2(H2L1)]n (3), [Ni2(bpm)(H2O)3(L2)]n (4), and {[Co2(H2O)3(OH)(HL2)]·H2O}n (5), (H4L1 = 1,1′:2′,1′′-terphenyl-4,4′,4′′,5′-tetracarboxylic acid, H4L2 = 1,1′:2′,1′′-terphenyl-3,3′′,4′,5′-tetracarboxylic acid, 2,2′-bipy = 2,2′-bipyridine, btb = 1,4-bis(1,2,4-triazol-1-yl)butane, bib = 1,4-bis(imidazol-1-yl)butane, bpm = bis(4-pyridyl)amine), have been obtained under hydrothermal conditions. Complex 1 exhibits a 3D supramolecular framework based on 1D chains. Both complexes 2 and 3 are 3D supramolecular frameworks constructed from 1D zig-zag chains. Complex 4 features a 3D tetra-nodal (3,4,4,5)-connected architecture containing 1D μ-COO bridged chains with (5(2)·6(2)·7.9)(5(2)·6(4)·7(3)·8)2(5(2)·6)2(6(3)·7(2)·9) topology. Complex 5 shows a 3D penta-nodal (3,4,4,6,6)-connected net containing 1D μ-OH/μ-COO bridged chains and mononuclear Co(II) nodes with a (4(2)·6(3)·8)(4(3))2(4(4)·6(2))2(4(4)·6(6)·8(5))2(4(4)·6(7)·8(4)) topology. Variable-temperature magnetic susceptibility measurements reveal that complexes 2 and 3 show antiferromagnetic interactions between the adjacent Co(II) ions, whereas 4 is a ferromagnetic system.

Thermally induced chain orientation for improved thermal conductivity of P(VDF-TrFE) thin films

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhao, Junnan; Tan, Aaron C.; Green, Peter F.

2017-01-01

A large increase in thermal conductivityκwas observed in a P(VDF-TrFE) thin film annealed above melting temperature due to extensive ordering of polymer backbone chains perpendicular to the substrate after recrystallization from the melt. This finding may lay out a straightforward method to improve the thin filmκof semicrystalline polymers whose chain orientation is sensitive to thermal annealing.

Precise control of polymer coated nanopores by nanoparticle additives: Insights from computational modeling

DOE Office of Scientific and Technical Information (OSTI.GOV)

Eskandari Nasrabad, Afshin; Coalson, Rob D.; Jasnow, David

Polymer-nanoparticle composites are a promising new class of materials for creation of controllable nano-patterned surfaces and nanopores. We use coarse-grained molecular dynamics simulations augmented with analytical theory to study the structural transitions of surface grafted polymer layers (brushes) induced by infiltration of nanoparticles that are attracted to the polymers in the layer. We systematically compare two different polymer brush geometries: one where the polymer chains are grafted to a planar surface and the other where the chains are grafted to the inside of a cylindrical nanochannel. We perform a comprehensive study of the effects of the material parameters such asmore » the polymer chain length, chain grafting density, nanoparticle size, strength of attraction between nanoparticles and polymer monomers, and, in the case of the cylindrically grafted brush, the radius of the cylinder. We find a very general behavioral motif for all geometries and parameter values: the height of the polymer brush is non-monotonic in the nanoparticle concentration in solution. As the nanoparticle concentration increases, the brush height first decreases and after passing through a minimum value begins to increase, resulting in the swelling of the nanoparticle infused brush. These morphological features may be useful for devising tunable “smart” nano-devices whose effective dimensions can be reversibly and precisely adjusted by changing the nanoparticle concentration in solution. The results of approximate Self-Consistent Field Theory (SCFT) calculations, applicable in the regime of strong brush stretching, are compared to the simulation results. The SCFT calculations are found to be qualitatively, even semi-quantitatively, accurate when applied within their intended regime of validity, and provide a useful and efficient tool for modeling such materials.« less

Size of the Dynamic Bead in Polymers

DOE Office of Scientific and Technical Information (OSTI.GOV)

Agapov, Alexander L; Sokolov, Alexei P

2010-01-01

Presented analysis of neutron, mechanical, and MD simulation data available in the literature demonstrates that the dynamic bead size (the smallest subchain that still exhibits the Rouse-like dynamics) in most of the polymers is significantly larger than the traditionally defined Kuhn segment. Moreover, our analysis emphasizes that even the static bead size (e.g., chain statistics) disagrees with the Kuhn segment length. We demonstrate that the deficiency of the Kuhn segment definition is based on the assumption of a chain being completely extended inside a single bead. The analysis suggests that representation of a real polymer chain by the bead-and-spring modelmore » with a single parameter C cannot be correct. One needs more parameters to reflect correctly details of the chain structure in the bead-and-spring model.« less

Local Chain Segregation and Entanglements in a Confined Polymer Melt

NASA Astrophysics Data System (ADS)

Lee, Nam-Kyung; Diddens, Diddo; Meyer, Hendrik; Johner, Albert

2017-02-01

The reptation mechanism, introduced by de Gennes and Edwards, where a polymer diffuses along a fluffy tube, defined by the constraints imposed by its surroundings, convincingly describes the relaxation of long polymers in concentrated solutions and melts. We propose that the scale for the tube diameter is set by local chain segregation, which we study analytically. We show that the concept of local segregation is especially operational for confined geometries, where segregation extends over mesoscopic domains, drastically reducing binary contacts, and provide an estimate of the entanglement length. Our predictions are quantitatively supported by extensive molecular dynamics simulations on systems consisting of long, entangled chains.

Why many polymers are so fragile: A new perspective

DOE PAGES

Dalle-Ferrier, C.; Kisliuk, A.; Hong, L.; ...

2016-10-21

Many polymers exhibit much steeper temperature dependence of their structural relaxation time (higher fragility) than liquids of small molecules, and the mechanism of this unusually high fragility in polymers remains a puzzle. To reveal additional hints for understanding the underlying mechanism, we analyzed correlation of many properties of polymers to their fragility on example of model polymer polystyrene with various molecular weights (MWs). Here, we demonstrate that these correlations work for short chains (oligomers), but fail progressively with increase in MW. Our surprising discovery is that the steepness of the temperature dependence (fragility) of the viscosity that is determined bymore » chain relaxation follows the correlations at all molecular weights. These results suggest that the molecular level relaxation still follows the behavior usual for small molecules even in polymers, and its fragility (chain fragility) falls in the range usual for molecular liquids. It is the segmental relaxation that has this unusually high fragility. We also speculate that many polymers cannot reach an ergodic state on the time scale of segmental dynamics due to chain connectivity and rigidity. This leads to sharper decrease in accessible configurational entropy upon cooling and results in steeper temperature dependence of segmental relaxation. Our proposed scenario provides a new important insight into the specifics of polymer dynamics: the role of ergodicity time and length scale. At the end, we suggest that a similar scenario can be applicable also to other molecular systems with slow intra-molecular degrees of freedom and to chemically complex systems where the time scale of chemical fluctuations can be longer than the time scale of structural relaxation.« less

Why many polymers are so fragile: A new perspective

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dalle-Ferrier, C.; Kisliuk, A.; Hong, L.

Many polymers exhibit much steeper temperature dependence of their structural relaxation time (higher fragility) than liquids of small molecules, and the mechanism of this unusually high fragility in polymers remains a puzzle. To reveal additional hints for understanding the underlying mechanism, we analyzed correlation of many properties of polymers to their fragility on example of model polymer polystyrene with various molecular weights (MWs). Here, we demonstrate that these correlations work for short chains (oligomers), but fail progressively with increase in MW. Our surprising discovery is that the steepness of the temperature dependence (fragility) of the viscosity that is determined bymore » chain relaxation follows the correlations at all molecular weights. These results suggest that the molecular level relaxation still follows the behavior usual for small molecules even in polymers, and its fragility (chain fragility) falls in the range usual for molecular liquids. It is the segmental relaxation that has this unusually high fragility. We also speculate that many polymers cannot reach an ergodic state on the time scale of segmental dynamics due to chain connectivity and rigidity. This leads to sharper decrease in accessible configurational entropy upon cooling and results in steeper temperature dependence of segmental relaxation. Our proposed scenario provides a new important insight into the specifics of polymer dynamics: the role of ergodicity time and length scale. At the end, we suggest that a similar scenario can be applicable also to other molecular systems with slow intra-molecular degrees of freedom and to chemically complex systems where the time scale of chemical fluctuations can be longer than the time scale of structural relaxation.« less

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 (V inv ) was positioned near the ideal switching point at half (1/2) of supplied voltage (V DD ) due to fairly balanced p- and n-channels.

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

PubMed

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

2016-08-10

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

Ion solvation in polymer blends and block copolymer melts: effects of chain length and connectivity on the reorganization of dipoles.

PubMed

Nakamura, Issei

2014-05-29

We studied the thermodynamic properties of ion solvation in polymer blends and block copolymer melts and developed a dipolar self-consistent field theory for polymer mixtures. Our theory accounts for the chain connectivity of polymerized monomers, the compressibility of the liquid mixtures under electrostriction, the permanent and induced dipole moments of monomers, and the resultant dielectric contrast among species. In our coarse-grained model, dipoles are attached to the monomers and allowed to rotate freely in response to electrostatic fields. We demonstrate that a strong electrostatic field near an ion reorganizes dipolar monomers, resulting in nonmonotonic changes in the volume fraction profile and the dielectric function of the polymers with respect to those of simple liquid mixtures. For the parameter sets used, the spatial variations near an ion can be in the range of 1 nm or larger, producing significant differences in the solvation energy among simple liquid mixtures, polymer blends, and block copolymers. The solvation energy of an ion depends substantially on the chain length in block copolymers; thus, our theory predicts the preferential solvation of ions arising from differences in chain length.

Nanostructure Control of Biologically Inspired Polymers

NASA Astrophysics Data System (ADS)

Rosales, Adrianne Marie

Biological polymers, such as polypeptides, are responsible for many of life's most sophisticated functions due to precisely evolved hierarchical structures. These protein structures are the result of monodisperse sequences of amino acids that fold into well-defined chain shapes and tertiary structures. Recently, there has been much interest in the design of such sequence-specific polymers for materials applications in fields ranging from biotechnology to separations membranes. Non-natural polymers offer the stability and robustness necessary for materials applications; however, our ability to control monomer sequence in non-natural polymers has traditionally operated on a much simpler level. In addition, the relationship between monomer sequence and self-assembly is not well understood for biological molecules, much less synthetic polymers. Thus, there is a need to explore self-assembly phase space with sequence using a model system. Polypeptoids are non-natural, sequence-specific polymers that offer the opportunity to probe the effect of sequence on self-assembly. A variety of monomer interactions have an impact on polymer properties, such as chirality, hydrophobicity, and electrostatic interactions. Thus, a necessary starting point for this project was to investigate monomer sequence effects on the bulk properties of polypeptoid homopolymers. It was found that several polypeptoids have experimentally accessible melting transitions that are dependent on the choice of side chains, and it was shown that this transition is tuned by the incorporation of "defects" or a comonomer. The polypeptoid chain shape is also controlled with the choice of monomer and monomer sequence. By using at least 50% monomers with bulky, chiral side chains, the polypeptoid backbone is sterically twisted into a helix, and as found for the first time in this work, the persistence length is increased. However, this persistence length, which is a measure of the stiffness of the polymer, is small compared to other folded helices, indicating the conformational flexibility of polypeptoid chains. With a firmer understanding of how monomer sequence and composition influence polypeptoid bulk properties, we designed block copolymer systems for self-assembly. Because the governing parameters of block copolymer self-assembly are well understood, this architecture provides a convenient starting point for probing the effect of changing polymer sequence. We found that polystyrene-polypeptoid block copolymers readily self-assemble into hexagonally-packed and lamellar morphologies with long range order, and furthermore, sequence control of the polypeptoid block enables us to tune the strength of segregation (and therefore the order-disorder transition) of the block copolymer. Polypeptoid chain shape also affects self-assembly. In classical synthetic block copolymers, it has typically been difficult to change chain shape without also changing polymer chemistry and therefore other factors affecting self-assembly. The advantage of the polypeptoid system is that it is modular, as the side chain chemistry (and therefore polymer properties) can easily be changed without changing the backbone chemistry. Thus, we have decoupled conformational effects from chemical composition by comparing the self-assembly of block copolymers containing either a helical peptoid block or its racemic, non-helical analog. The increase in the persistence length of the peptoid block due to helicity translates to an increase in the morphological domain spacing. In this work, we further the understanding of the effect of monomer sequence on bulk polypeptoid properties and self-assembly. Our findings pave the way for the rational design of structured synthetic polymers with tunable, sequence-specific properties.

Helmholtz and Gibbs ensembles, thermodynamic limit and bistability in polymer lattice models

NASA Astrophysics Data System (ADS)

Giordano, Stefano

2017-12-01

Representing polymers by random walks on a lattice is a fruitful approach largely exploited to study configurational statistics of polymer chains and to develop efficient Monte Carlo algorithms. Nevertheless, the stretching and the folding/unfolding of polymer chains within the Gibbs (isotensional) and the Helmholtz (isometric) ensembles of the statistical mechanics have not been yet thoroughly analysed by means of the lattice methodology. This topic, motivated by the recent introduction of several single-molecule force spectroscopy techniques, is investigated in the present paper. In particular, we analyse the force-extension curves under the Gibbs and Helmholtz conditions and we give a proof of the ensembles equivalence in the thermodynamic limit for polymers represented by a standard random walk on a lattice. Then, we generalize these concepts for lattice polymers that can undergo conformational transitions or, equivalently, for chains composed of bistable or two-state elements (that can be either folded or unfolded). In this case, the isotensional condition leads to a plateau-like force-extension response, whereas the isometric condition causes a sawtooth-like force-extension curve, as predicted by numerous experiments. The equivalence of the ensembles is finally proved also for lattice polymer systems exhibiting conformational transitions.

Polymer physics experiments with single DNA molecules

NASA Astrophysics Data System (ADS)

Smith, Douglas E.

1999-11-01

Bacteriophage DNA molecules were taken as a model flexible polymer chain for the experimental study of polymer dynamics at the single molecule level. Video fluorescence microscopy was used to directly observe the conformational dynamics of fluorescently labeled molecules, optical tweezers were used to manipulate individual molecules, and micro-fabricated flow cells were used to apply controlled hydrodynamic strain to molecules. These techniques constitute a powerful new experimental approach in the study of basic polymer physics questions. I have used these techniques to study the diffusion and relaxation of isolated and entangled polymer molecules and the hydrodynamic deformation of polymers in elongational and shear flows. These studies revealed a rich, and previously unobserved, ``molecular individualism'' in the dynamical behavior of single molecules. Individual measurements on ensembles of identical molecules allowed the average conformation to be determined as well as the underlying probability distributions for molecular conformation. Scaling laws, that predict the dependence of properties on chain length and concentration, were also tested. The basic assumptions of the reptation model were directly confirmed by visualizing the dynamics of entangled chains.

Self-Assembly of Emulsion Droplets into Polymer Chains

NASA Astrophysics Data System (ADS)

Bargteil, Dylan; McMullen, Angus; Brujic, Jasna

We experimentally investigate `beads-on-a-string' models of polymers using the spontaneous assembly of emulsion droplets into linear chains. Droplets functionalized with surface-mobile DNA allow for programmable 'monomers' through which we can influence the three-dimensional structure of the assembled 'polymer'. Such model polymers can be used to study conformational changes of polypeptides and the principles governing protein folding. In our system, we find that droplets bind via complementary DNA strands that are recruited into adhesion patches. Recruitment is driven by the DNA hybridization energy, and is limited by the energy cost of surface deformation and the entropy loss of the mobile linkers, yielding adhesion patches of a characteristic size with a given number of linkers. By tuning the initial surface coverage of linkers, we control valency between the droplets to create linear or branched polymer chains. We additionally control the flexibility of the model polymers by varying the salt concentration and study their dynamics between extended and collapsed states. This system opens the possibility of programming stable three-dimensional structures, such as those found within folded proteins.

Metal-Organic Polyhedral Core as a Versatile Scaffold for Divergent and Convergent Star Polymer Synthesis.

PubMed

Hosono, Nobuhiko; Gochomori, Mika; Matsuda, Ryotaro; Sato, Hiroshi; Kitagawa, Susumu

2016-05-25

We herein report the divergent and convergent synthesis of coordination star polymers (CSP) by using metal-organic polyhedrons (MOPs) as a multifunctional core. For the divergent route, copper-based great rhombicuboctahedral MOPs decorated with dithiobenzoate or trithioester chain transfer groups at the periphery were designed. Subsequent reversible addition-fragmentation chain transfer (RAFT) polymerization of monomers mediated by the MOPs gave star polymers, in which 24 polymeric arms were grafted from the MOP core. On the other hand, the convergent route provided identical CSP architectures by simple mixing of a macroligand and copper ions. Isophthalic acid-terminated polymers (so-called macroligands) immediately formed the corresponding CSPs through a coordination reaction with copper(II) ions. This convergent route enabled us to obtain miktoarm CSPs with tunable chain compositions through ligand mixing alone. This powerful method allows instant access to a wide variety of multicomponent star polymers that conventionally have required highly skilled and multistep syntheses. MOP-core CSPs are a new class of star polymer that can offer a design strategy for highly processable porous soft materials by using coordination nanocages as a building component.

Electrostatic stiffening and induced persistence length for coassembled molecular bottlebrushes

NASA Astrophysics Data System (ADS)

Storm, Ingeborg M.; Stuart, Martien A. Cohen; de Vries, Renko; Leermakers, Frans A. M.

2018-03-01

A self-consistent field analysis for tunable contributions to the persistence length of isolated semiflexible polymer chains including electrostatically driven coassembled deoxyribonucleic acid (DNA) bottlebrushes is presented. When a chain is charged, i.e., for polyelectrolytes, there is, in addition to an intrinsic rigidity, an electrostatic stiffening effect, because the electric double layer resists bending. For molecular bottlebrushes, there is an induced contribution due to the grafts. We explore cases beyond the classical phantom main-chain approximation and elaborate molecularly more realistic models where the backbone has a finite volume, which is necessary for treating coassembled bottlebrushes. We find that the way in which the linear charge density or the grafting density is regulated is important. Typically, the stiffening effect is reduced when there is freedom for these quantities to adapt to the curvature stresses. Electrostatically driven coassembled bottlebrushes, however, are relatively stiff because the chains have a low tendency to escape from the compressed regions and the electrostatic binding force is largest in the convex part. For coassembled bottlebrushes, the induced persistence length is a nonmonotonic function of the polymer concentration: For low polymer concentrations, the stiffening grows quadratically with coverage; for semidilute polymer concentrations, the brush chains retract and regain their Gaussian size. When doing so, they lose their induced persistence length contribution. Our results correlate well with observed physical characteristics of electrostatically driven coassembled DNA-bioengineered protein-polymer bottlebrushes.

Adsorbed Polymer Nanolayers on Solids: Mechanism, Structure and Applications

NASA Astrophysics Data System (ADS)

Sen, Mani Kuntal

In this thesis, by combining various advanced x-ray scattering, spectroscopic and other surface sensitive characterization techniques, I report the equilibrium polymer chain conformations, structures, dynamics and properties of polymeric materials at the solid-polymer melt interfaces. Following the introduction, in chapter 2, I highlight that the backbone chains (constituted of CH and CH2 groups) of the flattened polystyrene (PS) chains preferentially orient normal to the weakly interactive substrate surface via thermal annealing regardless of the initial chain conformations, while the orientation of the phenyl rings becomes randomized, thereby increasing the number of surface-segmental contacts (i.e., enthalpic gain) which is the driving force for the flattening process of the polymer chains even onto a weakly interactive solid. In chapter 3, I elucidate the flattened structures in block copolymer (BCP) thin films where both blocks lie flat on the substrate, forming a 2D randomly phase-separated structure irrespective of their microdomain structures and interfacial energetics. In chapter 4, I reveal the presence of an irreversibly adsorbed BCP layer which showed suppressed dynamics even at temperatures far above the individual glass transition temperatures of the blocks. Furthermore, this adsorbed BCP layer plays a crucial role in controlling the microdomain orientation in the entire film. In chapter 5, I report a radically new paradigm of designing a polymeric coating layer of a few nanometers thick ("polymer nanolayer") with anti-biofouling properties.

Synthesis and characterisation of new types of side chain cholesteryl polymers.

PubMed

Wang, Bin; Du, Haiyan; Zhang, Junhua

2011-01-01

A series of cholesterol derivatives have been synthesised via the alkylation reaction of the 3-hydroxyl group with the aliphatic bromide compounds with different chain lengths, namely 3β-alkyloxy-cholesterol. The double bond between the C5 and C6 positions in these cholesterol derivatives was oxidised into epoxy, followed by an epoxy-ring-opening reaction with the treatment with acrylic acid, resulting in a series of 3β-alkyloxy-5α-hydroxy-6β-acryloyloxycholesterol, C(n)OCh (n=1, 2, 4, 6, 8, 10, 12), The acrylate group is connected to the C6 position, which is confirmed by the single crystal structure analysis. The corresponding polymers, PC(n)OCh, were prepared via free radical polymerisation. The structure of monomers and the resulting polymers were characterised with nuclear magnetic resonance (NMR), Fourier transform infrared spectroscopy (FT-IR) and gel permeation chromatography (GPC). The thermal properties of PC(n)OCh were studied using differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). To determine the secondary structure of polymers, circular dichroism (CD) spectra were performed. It was found that not all monomers produce high-molecular-weight polymers because of steric hindrance. However, all polymers have a helical structure, which can be enhanced by increasing the alkoxy chain length. In addition, increasing the alkoxy chain length decreases the glass transition temperature and increases the decomposition temperature of the polymers. Copyright © 2010 Elsevier Inc. All rights reserved.

Symmetry Breaking in Side Chains Leading to Mixed Orientations and Improved Charge Transport in Isoindigo- alt -Bithiophene Based Polymer Thin Films

DOE Office of Scientific and Technical Information (OSTI.GOV)

Xue, Guobiao; Zhao, Xikang; Qu, Ge

The selection of side chains is important in design of conjugated polymers. It not only affects their intrinsic physical properties, but also has an impact on thin film morphologies. Recent reports suggested that a face-on/edge-on bimodal orientation observed in polymer thin films may be responsible for a three-dimensional (3D) charge transport and leads to dramatically improved mobility in donor–acceptor based conjugated polymers. To achieve a bimodal orientation in thin films has been seldom explored from the aspect of molecular design. Here, we demonstrate a design strategy involving the use of asymmetric side chains that enables an isoindigo-based polymer to adoptmore » a distinct bimodal orientation, confirmed by the grazing incidence X-ray diffraction. As a result, the polymer presents an average high mobility of 3.8 ± 0.7 cm2 V–1 s–1 with a maximum value of 5.1 cm2 V–1 s–1, in comparison with 0.47 and 0.51 cm2 V–1 s–1 obtained from the two reference polymers. This study exemplifies a new strategy to develop the next generation polymers through understanding the property-structure relationship.« less

Insight into the effect mechanism of urea-induced protein denaturation by dielectric spectroscopy.

PubMed

Zhang, Cancan; Yang, Man; Zhao, Kongshuang

2017-12-06

Dielectric relaxation spectroscopy was applied to study how urea affects the phase transition of a thermosensitive polymer, poly(N-isopropylacrylamide) (PNIPAM), which has been widely used as a protein model. It was found that there is a pronounced relaxation near 10 GHz for the ternary system of PNIPAM in urea aqueous solution. The temperature dependence of dielectric parameters indicates that urea can reduce the lower critical solution temperature (LCST) of PNIPAM, i.e., stabilize the globule state of PNIPAM and collapse the PNIPAM chains. Based on our results, the interaction mechanism of urea on the conformational transition of PNIPAM was presented: urea replaces water molecules directly bonding with PNIPAM and acts as the bridging agent for the adjacent side chains of PNIPAM. Accordingly, the mechanism with which urea denatures protein was deduced. In addition, it is worth mentioning that, from the temperature dependence of the dielectric parameters obtained in the presence of urea, an interesting phenomenon was found in which the effect of urea on PNIPAM seems to take 2 M as a unit. This result may be the reason why urea and TMAO exit marine fishes at a specific ratio of 2 : 1.

The stability of cellulose: a statistical perspective from a coarse-grained model of hydrogen-bond networks.

PubMed

Shen, Tongye; Gnanakaran, S

2009-04-22

A critical roadblock to the production of biofuels from lignocellulosic biomass is the efficient degradation of crystalline microfibrils of cellulose to glucose. A microscopic understanding of how different physical conditions affect the overall stability of the crystalline structure of microfibrils could facilitate the design of more effective protocols for their degradation. One of the essential physical interactions that stabilizes microfibrils is a network of hydrogen (H) bonds: both intrachain H-bonds between neighboring monomers of a single cellulose polymer chain and interchain H-bonds between adjacent chains. We construct a statistical mechanical model of cellulose assembly at the resolution of explicit hydrogen-bond networks. Using the transfer matrix method, the partition function and the subsequent statistical properties are evaluated. With the help of this lattice-based model, we capture the plasticity of the H-bond network in cellulose due to frustration and redundancy in the placement of H-bonds. This plasticity is responsible for the stability of cellulose over a wide range of temperatures. Stable intrachain and interchain H-bonds are identified as a function of temperature that could possibly be manipulated toward rational destruction of crystalline cellulose.

Effect of chain stiffness on the competition between crystallization and glass-formation in model unentangled polymers

NASA Astrophysics Data System (ADS)

Nguyen, Hong T.; Smith, Tyler B.; Hoy, Robert S.; Karayiannis, Nikos Ch.

2015-10-01

We map out the solid-state morphologies formed by model soft-pearl-necklace polymers as a function of chain stiffness, spanning the range from fully flexible to rodlike chains. The ratio of Kuhn length to bead diameter (lK/r0) increases monotonically with increasing bending stiffness kb and yields a one-parameter model that relates chain shape to bulk morphology. In the flexible limit, monomers occupy the sites of close-packed crystallites while chains retain random-walk-like order. In the rodlike limit, nematic chain ordering typical of lamellar precursors coexists with close-packing. At intermediate values of bending stiffness, the competition between random-walk-like and nematic chain ordering produces glass-formation; the range of kb over which this occurs increases with the thermal cooling rate | T ˙ | implemented in our molecular dynamics simulations. Finally, values of kb between the glass-forming and rodlike ranges produce complex ordered phases such as close-packed spirals. Our results should provide a useful initial step in a coarse-grained modeling approach to systematically determining the effect of chain stiffness on the crystallization-vs-glass-formation competition in both synthetic and colloidal polymers.

BET, thermal degradation, and FTIR spectras of triazine polyamine polymers.

PubMed

Can, Mustafa

2017-04-01

Here we show effect of the polyamine polymer chain length to BET isotherms. According to IUPAC classification [1], all three polymers are fitting type 1 physical adsorption isotherm with H3 hysteresis (except for EDA having H2 hysteresis). Moreover, TG and TGA analysis of polymers triazine-ethylenediamine (EDA) and triazine-triethylenetetramine (TETA) are provided. Due to the similarities of the structure, main decomposition temperatures are close to each other (between 593 K and 873 K). In order to understand change of FTIR spectra with adsorption and stripping Au(III), fresh, Au(III) adsorbed and recycled spectras of polymers measured. For further discussions about the effect of chain length to adsorption of Au(III) onto triazine polyamine polymer particles "Au (III) Uptake by Triazine Polyamine Polymers: Mechanism, Kinetic and Equilibrium Studies" Can et al. [2] (article in press).

Folding dynamics of linear emulsion polymers into 3D architectures

NASA Astrophysics Data System (ADS)

McMullen, Angus; Bargteil, Dylan; Brujic, Jasna

Colloidal polymers have been limited to inflexible, solid colloids. Here we show that the fluidity of emulsion droplets allows for the self-assembly of flexible droplet chains, which can subsequently be folded into 3D structures via secondary interactions. We achieve this using DNA-guided interactions, to initially form the chain, and then program its folding pathways. When two emulsion droplets labeled with complementary DNA meet, the balance of hybridization energy and droplet deformation yields an equilibrium patch size. Therefore, the concentration of DNA on the surface determines the number of droplet-droplet bonds in the assembly. We find that 96 % of bound droplets successfully self-assemble into chains. Droplet binding is a stochastic process, following a Poisson distribution of lengths. Since the fluid droplets can rearrange, we compare the dynamics of emulsion chains to that of polymers. We also trigger secondary interactions along the chain, causing the formation of specific loops or compact clusters. This approach will allow us to fold our emulsion polymers into a wide array of soft structures, giving us a powerful biomimetic colloidal system to investigate protein folding on the mesoscopic scale. This work was supported by the NSF MRSEC Program (DMR-0820341).

Rouse mode analysis of chain relaxation in polymer nanocomposites

DOE PAGES

Kalathi, Jagannathan T.; Kumar, Sanat K.; Rubinstein, Michael; ...

2015-04-20

Large-scale molecular dynamics simulations are used to study the internal relaxations of chains in nanoparticle (NP)/polymer composites. We examine the Rouse modes of the chains, a quantity that is closest in spirit to the self-intermediate scattering function, typically determined in an (incoherent) inelastic neutron scattering experiment. Our simulations show that for weakly interacting mixtures of NPs and polymers, the effective monomeric relaxation rates are faster than in a neat melt when the NPs are smaller than the entanglement mesh size. In this case, the NPs serve to reduce both the monomeric friction and the entanglements in the polymer melt, asmore » in the case of a polymer–solvent system. However, for NPs larger than half the entanglement mesh size, the effective monomer relaxation is essentially unaffected for low NP concentrations. Even in this case, we observe a strong reduction in chain entanglements for larger NP loadings. Furthermore, the role of NPs is to always reduce the number of entanglements, with this effect only becoming pronounced for small NPs or for high concentrations of large NPs. Our studies of the relaxation of single chains resonate with recent neutron spin echo (NSE) experiments, which deduce a similar entanglement dilution effect.« less

Self organized striping in ultra thin polymer films near melt: An investigation using Monte Carlo simulation

NASA Astrophysics Data System (ADS)

Singh, Satya Pal

2018-05-01

This paper work presents the results of Monte Carlo simulation performed for ultra thin short chained polymer films near melt, under strong confinement. Thin polymer films get ruptured when annealed above their glass transition temperatures. The pattern formations are generally explained on the basis of spinodal mechanism, if the thickness of the film is of the order of few tens of nanometers i.e. <100 nm. In this case, the film seems to tear apart in strips. The free end segments of the chains are more dynamic and coalescence into one another. This process seems to dominate over the spinodal waves resulting into a different type of dynamics. Polymer chains with 30 monomers are taken. 160, 200 and 240 chains are taken for three different cases of the studies. The three cases correspond to three different thickness of the films with 8, 10 and 12 layers of chains along direction perpendicular to the confining substrates. The bottom surface has affinity to monomers, whereas the upper surface has hard wall interaction with the monomers. Different time micrographs of the films are plotted along with density distributions of the monomers to explore the process.

Nanostructures and dynamics of macromolecules bound to attractive filler surfaces

NASA Astrophysics Data System (ADS)

Koga, Tad; Barkley, Deborah; Jiang, Naisheng; Endoh, Maya; Masui, Tomomi; Kishimoto, Hiroyuki; Nagao, Michihiro; Satija, Sushil; Taniguchi, Takashi

We report in-situ nanostructures and dynamics of polybutadiene (PB) chains bound to carbon black (CB) fillers (the so-called ``bound polymer layer (BPL)'') in a good solvent. The BPL on the CB fillers were extracted by solvent leaching of a CB-filled PB compound and subsequently dispersed in deuterated toluene to label the BPL for small-angle neutron scattering and neutron spin echo techniques. Intriguingly, the results demonstrate that the BPL is composed of two regions regardless of molecular weights of PB: the inner unswollen region of ~ 0.5 nm thick and outer swollen region where the polymer chains display a parabolic profile with a diffuse tail. This two-layer formation on the filler surface is similar to that reported for polymer chains adsorbed on planar substrates from melts. In addition, the results show that the dynamics of the swollen bound chains can be explained by the so-called ``breathing mode'' and is generalized with the thickness of the swollen BPL. Furthermore, we will discuss how the breathing collective dynamics is affected by the presence of polymer chains in a matrix solution. We acknowledge the financial support from NSF Grant No. CMMI-1332499.

Thermal aging of interfacial polymer chains in ethylene-propylene-diene terpolymer/aluminum hydroxide composites: solid-state NMR study.

PubMed

Gabrielle, Brice; Lorthioir, Cédric; Lauprêtre, Françoise

2011-11-03

The possible influence of micrometric-size filler particles on the thermo-oxidative degradation behavior of the polymer chains at polymer/filler interfaces is still an open question. In this study, a cross-linked ethylene-propylene-diene (EPDM) terpolymer filled by aluminum trihydrate (ATH) particles is investigated using (1)H solid-state NMR. The time evolution of the EPDM network microstructure under thermal aging at 80 °C is monitored as a function of the exposure time and compared to that of an unfilled EPDM network displaying a similar initial structure. While nearly no variations of the topology are observed on the neat EPDM network over 5 days at 80 °C, a significant amount of chain scission phenomena are evidenced in EPDM/ATH. A specific surface effect induced by ATH on the thermodegradative properties of the polymer chains located in their vicinity is thus pointed out. Close to the filler particles, a higher amount of chain scissions are detected, and the characteristic length scale related to these interfacial regions displaying a significant thermo-oxidation process is determined as a function of the aging time.

Alternative Fluoropolymers to Avoid the Challenges Associated with Perfluorooctanoic Acid

DOE Office of Scientific and Technical Information (OSTI.GOV)

Guo,J.; Resnick, P.; Efimenko, K.

2008-01-01

The degradation of stain-resistant coating materials leads to the release of biopersistent perfluorooctanoic acid (PFOA) to the environment. In order to find the environmentally friendly substitutes, we have designed and synthesized a series of nonbiopersistant fluorinated polymers containing perfluorobutyl groups in the side chains. The surface properties of the new coating materials were characterized by static and dynamic contact angle measurements. The new coating materials demonstrate promising hydrophobic and oleophobic properties with low surfaces tensions. The wetting properties and surface structure of the polymers were tuned by varying the 'spacer' structures between the polymer backbones and the perfluorinated groups ofmore » the side chains. The relationship between orientations of the fluorinated side chains and performances of polymer surfaces were further investigated by near-edge X-ray fine absorption structure (NEXAFS) experiments and differential scanning calorimetry (DSC).« less

Self-Organization of Polymer Brush Layers in a Poor Solvent

NASA Astrophysics Data System (ADS)

Karim, A.; Tsukruk, V. V.; Douglas, J. F.; Satija, S. K.; Fetters, L. J.; Reneker, D. H.; Foster, M. D.

1995-10-01

Synthesis of densely grafted polymer brushes from good solvent polymer solutions is difficult when the surface interaction is only weakly attractive because of the strong steric repulsion between the polymer chains. To circumvent this difficulty we graft polymer layers in a poor solvent to exploit attractive polymer-polymer interactions which largely nullify the repulsive steric interactions. This simple strategy gives rise to densely grafted and homogeneous polymer brush layers. Model end-grafted polystyrene chains (M_w = 105,000) are prepared in the poor solvent cyclohexane (9.5 °C) where the chains are chemically attached to the surface utilizing a trichlorosilane end-group. Polished silicon wafers were then exposed to the reactive polymer solutions for a series of “induction times” tau_I and the evolving layer was characterized by X-ray reflectivity and atomic force microscopy. Distinct morphologies were found depending on tau_I. For short tau_I, corresponding to a grafting density less than 5 mg/m^2, the grafted layer forms an inhomogeneous island-like structure. At intermediate tau_I, where the coverage becomes percolating, a surface pattern develops which appears similar to spinodal decomposition in bulk solution. Finally, after sufficiently long tau_I, a dense and nearly homogeneous layer with a sharp interface is formed which does not exhibit surface pattern formation. The stages of brush growth are discussed qualitatively in terms of a random deposition model.

On the simulation and theory of polymer dynamics in sieving media: Friction, molecular pulleys, Brownian ratchets and polymer scission

NASA Astrophysics Data System (ADS)

Kenward, Martin

The study of single polymer dynamics has, in the past few years, undergone a resurgence. This has been spurred on by the emergence of the fields of micro- and nanofluidics and their associated applications, especially by their ability to promise revolutionary techniques to, for example: rapidly sequence DNA, analyze proteins, carry out large-scale laboratory techniques in centimeter sized devices (lab-on-a-chip) and test and verify fundamental concepts related to the statistical physics of single molecules in fluids. In particular, the study of (typically single, isolated) polymers and the development of theoretical methods and computational tools to examine these polymers in microfluidic environments is a key challenge. In this thesis, we examine several different phenomena related to the dynamics of polymers in either microfluidic environments or related applications to DNA sequencing or separation. A recurrent theme throughout this work is the use of Molecular Dynamics (MD) simulations with an explicit solvent. Explicit solvent is an important aspect of our simulations and contrasts much work in the current literature which either artificially includes solvent or neglects it all together. This explicit inclusion of solvent allows us to explore phenomena (related to hydrodynamics) that is not observable with, for example, Brownian (or Langevin) Dynamics or Monte Carlo simulations. Chapter 2 contains a primarily computational examination of the friction coefficients of uncharged polymers. We explore the effects of deforming polymer chains on their friction coefficients along with examining several fundamental concepts of polymer friction (including hydrodynamic permeability). A key result is a verification of the hydrodynamic coupling of polymer chains resulting from a net reduction in the friction of polymer chains in hairpin (or folded) conformations. We also show that polymers undergo frictional transitions as they are stretched by an external force applied to the middle of the molecules. In chapter 3 we use some of the concepts and results from chapters 1 and 2 to explore the problem of a polymer chain migrating under the influence of an external force (or fluid flow) through a molecular obstacle course. These polymers collide with either fixed obstacles (or other polymers) and can be trapped in meta-stable long-lived, pulley-like conformations. This method can be used to separate polymers by molecular weight. We use both MD simulations and a general classical theory for the collisions to explore several different collision regimes. We also show that a classic experimental result, the formation of so-called V-shaped states, can occur in single polymer collision events, contrary to the popular assumption that it was necessary for a polymer to collide with multiple polymers. In chapter 4 we build on the results and ideas from the first three chapters and examine another phenomenon related to polymer transport, that of (Brownian) ratchets. A ratchet is essentially a method to rectify the thermal noise in a system in order to perform work, for example, to generate net transport. We use our MD simulations to examine the behaviour of polymers in the presence of an asymmetric saw tooth ratchet potential. We also show that existing ratchet models, where the ratchet widths are on the order of a polymer gyration radius, neglect an important effect of chain relaxation and thus underestimate optimal operating parameters. We propose and derive equations illustrating a new operational mode for a ratchet which inherently uses the deformation of polymer chains induced by the application of a ratcheting potential. We present a simple mathematical expression to incorporate time-dependent diffusion coefficients D (t) into ratchets. The final chapter presents work done in collaboration with Annelise Barron's group at Northwestern University and examines the breaking of polymer chains in extensional flow fields as a method to systematically and predictably reduce the polydispersity (PDI) of polymer solutions. The experimental investigation, carried out by the Barron group illustrated that a dilute polymer solution, when passed through a narrow constriction at high pressure can systematically reduce the PDI of the polymer solution. My contribution to this work was to develop a statistical model which calculates polymer molecular weight distributions and which can predict the resulting degraded polymer distribution. Two key things resulted from this investigation, the first is that polymers can break multiple times during a single scission event (i.e., one pass through the experimental system). Secondly we showed that it is possible to predictably reproduce polymer distributions after multiple scission events.

Smectic order and backbone anisotropy of a side-chain liquid crystalline polymer by Small-Angle Neutron Scattering

NASA Astrophysics Data System (ADS)

Noirez, L.; Pépy, G.; Keller, P.; Benguigui, L.

1991-07-01

We have simultaneously measured, for the first time, the extension of the polymer backbone of a side-chain liquid crystalline polymer and the intensity of the 001 Bragg reflection, which gives the smectic order parameter Psi as a function of temperature in the smectic phase. We have qualitatively demonstrated that the more the smectic phase is ordered, the more the polymer backbone is localized between the mesogenic layers. It is shown that the Landau theory allows us to relate the radius of gyration parallel to the magnetic field of the polymer backbone to the smectic order parameter. We also show that the Renz-Warner theory is suitable at low temperatures.

Electrode assembly for use in a solid polymer electrolyte fuel cell

DOEpatents

Raistrick, Ian D.

1989-01-01

A gas reaction fuel cell may be provided with a solid polymer electrolyte membrane. Porous gas diffusion electrodes are formed of carbon particles supporting a catalyst which is effective to enhance the gas reactions. The carbon particles define interstitial spaces exposing the catalyst on a large surface area of the carbon particles. A proton conducting material, such as a perfluorocarbon copolymer or ruthenium dioxide contacts the surface areas of the carbon particles adjacent the interstitial spaces. The proton conducting material enables protons produced by the gas reactions adjacent the supported catalyst to have a conductive path with the electrolyte membrane. The carbon particles provide a conductive path for electrons. A suitable electrode may be formed by dispersing a solution containing a proton conducting material over the surface of the electrode in a manner effective to coat carbon surfaces adjacent the interstitial spaces without impeding gas flow into the interstitial spaces.

Functional lignocellulosic materials prepared by ATRP from a wood scaffold.

PubMed

Cabane, Etienne; Keplinger, Tobias; Künniger, Tina; Merk, Vivian; Burgert, Ingo

2016-08-10

Wood, a natural and abundant source of organic polymers, has been used as a scaffold to develop novel wood-polymer hybrid materials. Through a two-step surface-initiated Atom Transfer Radical Polymerization (ATRP), the porous wood structure can be effectively modified with polymer chains of various nature. In the present study, polystyrene and poly(N-isopropylacrylamide) were used. As shown with various characterization techniques including confocal Raman microscopy, FTIR, and SEM/EDX, the native wood ultrastructure and features are retained and the polymer chains can be introduced deep within the wood, i.e. inside the wood cell walls. The physical properties of the new materials have been studied, and results indicate that the insertion of polymer chains inside the wood cell wall alters the intrinsic properties of wood to yield a hybrid composite material with new functionalities. This approach to the functionalization of wood could lead to the fabrication of a new class of interesting functional materials and promote innovative utilizations of the renewable resource wood.

Functional lignocellulosic materials prepared by ATRP from a wood scaffold

PubMed Central

Cabane, Etienne; Keplinger, Tobias; Künniger, Tina; Merk, Vivian; Burgert, Ingo

2016-01-01

Wood, a natural and abundant source of organic polymers, has been used as a scaffold to develop novel wood-polymer hybrid materials. Through a two-step surface-initiated Atom Transfer Radical Polymerization (ATRP), the porous wood structure can be effectively modified with polymer chains of various nature. In the present study, polystyrene and poly(N-isopropylacrylamide) were used. As shown with various characterization techniques including confocal Raman microscopy, FTIR, and SEM/EDX, the native wood ultrastructure and features are retained and the polymer chains can be introduced deep within the wood, i.e. inside the wood cell walls. The physical properties of the new materials have been studied, and results indicate that the insertion of polymer chains inside the wood cell wall alters the intrinsic properties of wood to yield a hybrid composite material with new functionalities. This approach to the functionalization of wood could lead to the fabrication of a new class of interesting functional materials and promote innovative utilizations of the renewable resource wood. PMID:27506369

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

DTIC Science & Technology

2014-10-15

led to lower PL efficiencies. The latter, however, posed no problems for solar cells aplications . Furthermore, the molecular dipoles composed of...illuminated under the light of the energy falling in the absorption range of the conjugated polymer, the polymer chain mobility decreased...the other hand, increased concomitantly (Figs. 33, 35). The driving force for the molecular flows is the diffusion of the mobile PS chains toward

Heat conduction in chain polymer liquids: molecular dynamics study on the contributions of inter- and intramolecular energy transfer.

PubMed

Ohara, Taku; Yuan, Tan Chia; Torii, Daichi; Kikugawa, Gota; Kosugi, Naohiro

2011-07-21

In this paper, the molecular mechanisms which determine the thermal conductivity of long chain polymer liquids are discussed, based on the results observed in molecular dynamics simulations. Linear n-alkanes, which are typical polymer molecules, were chosen as the target of our studies. Non-equilibrium molecular dynamics simulations of bulk liquid n-alkanes under a constant temperature gradient were performed. Saturated liquids of n-alkanes with six different chain lengths were examined at the same reduced temperature (0.7T(c)), and the contributions of inter- and intramolecular energy transfer to heat conduction flux, which were identified as components of heat flux by the authors' previous study [J. Chem. Phys. 128, 044504 (2008)], were observed. The present study compared n-alkane liquids with various molecular lengths at the same reduced temperature and corresponding saturated densities, and found that the contribution of intramolecular energy transfer to the total heat flux, relative to that of intermolecular energy transfer, increased with the molecular length. The study revealed that in long chain polymer liquids, thermal energy is mainly transferred in the space along the stiff intramolecular bonds. This finding implies a connection between anisotropic thermal conductivity and the orientation of molecules in various organized structures with long polymer molecules aligned in a certain direction, which includes confined polymer liquids and self-organized structures such as membranes of amphiphilic molecules in water.

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.

End-anchored polymers in good solvents from the single chain limit to high anchoring densities.

PubMed

Whitmore, Mark D; Grest, Gary S; Douglas, Jack F; Kent, Michael S; Suo, Tongchuan

2016-11-07

An increasing number of applications utilize grafted polymer layers to alter the interfacial properties of solid substrates, motivating refinement in our theoretical understanding of such layers. To assess existing theoretical models of them, we have investigated end-anchored polymer layers over a wide range of grafting densities, σ, ranging from a single chain to high anchoring density limits, chain lengths ranging over two orders of magnitude, for very good and marginally good solvent conditions. We compare Monte Carlo and molecular dynamics simulations, numerical self-consistent field calculations, and experimental measurements of the average layer thickness, h, with renormalization group theory, the Alexander-de Gennes mushroom theory, and the classical brush theory. Our simulations clearly indicate that appreciable inter-chain interactions exist at all simulated areal anchoring densities so that there is no mushroom regime in which the layer thickness is independent of σ. Moreover, we find that there is no high coverage regime in which h follows the predicted scaling, h ∼ Nσ 1/3 , for classical polymer brushes either. Given that no completely adequate analytic theory seems to exist that spans wide ranges of N and σ, we applied scaling arguments for h as a function of a suitably defined reduced anchoring density, defined in terms of the solution radius of gyration of the polymer chains and N. We find that such a scaling approach enables a smooth, unified description of h in very good solvents over the full range of anchoring density and chain lengths, although this type of data reduction does not apply to marginal solvent quality conditions.

Crosslinked polymer nanoparticles containing single conjugated polymer chains

NASA Astrophysics Data System (ADS)

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

2017-06-01

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

Correlation functions of main-chain polymer nematics constrained by tensorial and vectorial conservation laws

NASA Astrophysics Data System (ADS)

Svenšek, Daniel; Podgornik, Rudolf

2015-09-01

We present and analyze correlation functions of a main-chain polymer nematic in a continuum worm-like chain description for two types of constraints formalized by the tensorial and vectorial conservation laws, both originating in the microscopic chain integrity, i.e., the connectivity of the polymer chains. In particular, our aim is to identify the features of the correlation functions that are most susceptible to the differences between the two constraints. Besides the density and director autocorrelations in both the tensorial and vectorial cases, we calculate also the density-director correlation functions, the latter being a direct signature of the presence of a specific constraint. Its amplitude is connected to the strength of the constraint and is zero if none of the constraints are present, i.e., for a standard non-polymeric nematic. Generally, the correlation functions with the constraints differ substantially from the correlation functions in the non-polymeric case, if the constraints are strong which in practice requires long chains. Moreover, for the tensorial conservation law to be well distinguishable from the vectorial one, the chain persistence length should be much smaller than the total length of the chain, so that hairpins (chain backfolding) are numerous and the polar order is small.

Crystal structure and charge transport properties of poly(arylene-ethynylene) derivatives: A DFT approach

NASA Astrophysics Data System (ADS)

Garzón, Andrés; Granadino-Roldán, José M.; García, Gregorio; Moral, Mónica; Fernández-Gómez, Manuel

2013-04-01

In the present study, a series of crystalline poly(arylene-ethynylene) copolymers containing phenylethynylene and 2,5-dialkoxy-phenylethynylene units together with 1,3,4-thiadiazole rings has been modeled by means of periodic calculations. Optimized three-dimensional polymeric structures show interchain distances that are consistent with the experimental values reported for a related polymer. It has also been observed that the presence of pendant alkoxy chains brings on both a further flattening and a separation of the coplanar chains. This fact is linked to a decrease of the interchain cofacial distance. The electron transport character of the polymer crystal structures was assessed through Marcus theory. Electronic coupling between neighboring polymer chains is most influenced by the presence of alkoxy chains giving rise to an expectable enhancement of the electron hopping mobility.

Hydrophilization and hydrophobic recovery in polymers obtained by casting of polymer solutions on water surface.

PubMed

Bormashenko, Edward; Chaniel, Gilad; Gendelman, Oleg

2014-12-01

We demonstrate the possibility of hydrophilization of polymer films in situ under the process of their preparation. The polymer surface is hydrophilized when the polymer solution is spread on the water surface and the solvent is evaporated. Essential hydrophilization of the polymer surface is achieved under this process. We relate the observed hydrophilization of polymer films to the dipole-dipole interaction of the polar moieties of polymer chains with highly polar water molecules. The dipole-dipole interaction between water molecules and polar groups of polymer chains, orienting the polar groups of a polymer, may prevail over the London dispersion forces. The process, reported in the paper, allows to manufacture the films in which the hydrophilic moieties of the polymer molecule are oriented toward the polymer/air interface. It is demonstrated that even such traditionally extremely hydrophobic polymers as polydimethylsiloxane can be markedly hydrophilized. This hydrophilization, however, does not persist forever. After removal from the water surface, hydrophobic recovery was observed, i.e. polymer films restored their hydrophobicity with time. The characteristic time of the hydrophobic recovery is on the order of magnitude of hours. Copyright © 2014 Elsevier Inc. All rights reserved.

A constitutive law for degrading bioresorbable polymers.

PubMed

Samami, Hassan; Pan, Jingzhe

2016-06-01

This paper presents a constitutive law that predicts the changes in elastic moduli, Poisson's ratio and ultimate tensile strength of bioresorbable polymers due to biodegradation. During biodegradation, long polymer chains are cleaved by hydrolysis reaction. For semi-crystalline polymers, the chain scissions also lead to crystallisation. Treating each scission as a cavity and each new crystal as a solid inclusion, a degrading semi-crystalline polymer can be modelled as a continuum solid containing randomly distributed cavities and crystal inclusions. The effective elastic properties of a degrading polymer are calculated using existing theories for such solid and the tensile strength of the degrading polymer is predicted using scaling relations that were developed for porous materials. The theoretical model for elastic properties and the scaling law for strength form a complete constitutive relation for the degrading polymers. It is shown that the constitutive law can capture the trend of the experimental data in the literature for a range of biodegradable polymers fairly well. Copyright © 2016 Elsevier Ltd. All rights reserved.

Synthesis and redox activity of "clicked" triazolylbiferrocenyl polymers, network encapsulation of gold and silver nanoparticles and anion sensing.

PubMed

Rapakousiou, Amalia; Deraedt, Christophe; Irigoyen, Joseba; Wang, Yanlan; Pinaud, Noël; Salmon, Lionel; Ruiz, Jaime; Moya, Sergio; Astruc, Didier

2015-03-02

The design of redox-robust polymers is called for in view of interactions with nanoparticles and surfaces toward applications in nanonetwork design, sensing, and catalysis. Redox-robust triazolylbiferrocenyl (trzBiFc) polymers have been synthesized with the organometallic group in the side chain by ring-opening metathesis polymerization using Grubbs-III catalyst or radical polymerization and with the organometallic group in the main chain by Cu(I) azide alkyne cycloaddition (CuAAC) catalyzed by [Cu(I)(hexabenzyltren)]Br. Oxidation of the trzBiFc polymers with ferricenium hexafluorophosphate yields the stable 35-electron class-II mixed-valent biferrocenium polymer. Oxidation of these polymers with Au(III) or Ag(I) gives nanosnake-shaped networks (observed by transmission electron microscopy and atomic force microscopy) of this mixed-valent Fe(II)Fe(III) polymer with encapsulated metal nanoparticles (NPs) when the organoiron group is located on the side chain. The factors that are suggested to be synergistically responsible for the NP stabilization and network formation are the polymer bulk, the trz coordination, the nearby cationic charge of trzBiFc, and the inter-BiFc distance. For instance, reduction of such an oxidized trzBiFc-AuNP polymer to the neutral trzBiFc-AuNP polymer with NaBH4 destroys the network, and the product flocculates. The polymers easily provide modified electrodes that sense, via the oxidized Fe(II)Fe(III) and Fe(III)Fe(III) polymer states, respectively, ATP(2-) via the outer ferrocenyl units of the polymer and Pd(II) via the inner Fc units; this recognition works well in dichloromethane, but also to a lesser extent in water with NaCl as the electrolyte.

Exploring ways to control the properties of polymer thin films

NASA Astrophysics Data System (ADS)

Clough, Andrew R.

Understanding the causes of deviations from bulk-like properties observed in polymer thin films is of interest both from a fundamental standpoint and in order to tailor the properties of polymer thin films used by industry as coatings and in the production of microelectronic devices. As thicknesses are decreased below 100 nm, interfacial effects start to become important. In addition, a confinement effect occurs when the film thickness becomes comparable to the unperturbed size of the polymer chain. In this thesis, we modify polymer films in a controllable way in order to study how some of these properties may be related and potentially adjusted. One of these properties is the glass transition temperature, which is seen to vary with the film thickness for films thinner than 100 nm. While there appears to be a consensus that the variation is attributable to the interactions the polymer has with the film interfaces, important questions concerning how the observed changes may affect the onset of large scale, liquid-like motions in the films have been seldom investigated. We modify the substrate interface with grafted polymer chains, which is known to instill interfacial slippage, to investigate the relation, if any, between the glass transition temperature and large scale chain motions in the films. As another part of the effort to find ways to control the properties of polymer films, we study the effect of swelling films with solvents of different qualities. Studies have shown that modifying the solvent quality used when preparing films by spin-coating, in which solvent from a polymer solution is rapidly removed to form thin uniform films, can affect some properties by modifying the degree of inter-chain entanglement in the film. As it is often difficult to spin-coat films when the solvent is poor, we investigate whether solvent swelling can also be used to modify this entanglement. We find that solvent swelling is able to modify the degree of entanglement in the films. Most importantly, swelling with a poor solvent allows us to reduce the degree of inter-chain entanglement, bringing the film further from equilibrium.

Effects of nanoscale aggregation on mechanical properties and local dynamics of precise acid- and ion-containing polymers

NASA Astrophysics Data System (ADS)

Middleton, Luri Robert

Acid- and ion-containing polymers have interchain interactions that alter polymer behavior at the nano, micro, and bulk length scales. Strong secondary-bonds act as thermo-reversible physical crosslinks between chains which drive self-assembly. Tuning theses interactions can modify bulk polymer properties including stiffness, toughness, melt viscosity, resilience, clarity, abrasion resistance and puncture resistance. Furthermore, understanding and improving the relevant factors that control transport properties would have vast implications on developing solid polymer electrolytes (SPEs) for technologically important applications including water desalination, ion exchange membranes and microelectronics. This thesis explores the structure - processing - morphology - property relationships of acid and ionic functionalized polymers. Improvements in synthetic techniques and advancements in characterization methods have enabled new studies of associating polymer systems. Synthesis of entangled, high molecular weight, linear polyethylene (PE) chains functionalized with interacting pendant groups (acidic or ionic) placed periodically along the polymer backbone represent a new class of associating polymers. These polymers with periodic distributions of acid groups are much more homogenous than the commercially available polymers. Previous studies of these polymers with greater structural homogeneity revealed great variety in morphologies of the nano-aggregated polar groups within the non-polar polymer matrix. This thesis correlated the morphologies with bulk properties through real-time X-ray scattering and tensile deformation at a range of temperatures and sample compositions. New, transient morphologies and hierarchical morphologies were observed which coincided with unusual tensile strain hardening. These results indicate that improvements in synthetic control of polymers can enhance physical properties such as tensile strain-hardening, through cooperative bonding between chains. The structural regularity of precise polyethylenes also enables robust comparisons between experiments and computer simulations. At pico- to nano-seconds time scales and length scales of polymer and aggregate dynamics, neutron scattering and molecular dynamics simulations were combined to extend the knowledge of the molecular-level aggregated polymer dynamics. These experiments provide a baseline for future studies of ion-conduction in associating polymer melts.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Shen, Yong; Desseaux, Solenne; Aden, Bethany

We report that surface-grafting thermoresponsive polymers allows the preparation of thin polymer brush coatings with surface properties that can be manipulated by variation of temperature. In most instances, thermoresponsive polymer brushes are produced using polymers that dehydrate and collapse above a certain temperature. This report presents the preparation and properties of polymer brushes that show thermoresponsive surface properties, yet are shape-persistent in that they do not undergo main chain collapse. The polymer brushes presented here are obtained via vapor deposition surface-initiated ring-opening polymerization (SI-ROP) of γ-di- or tri(ethylene glycol)-modified glutamic acid N-carboxyanhydrides. Vapor deposition SI-ROP of γ-di- or tri(ethylene glycol)-modifiedmore » L- or D-glutamic acid N-carboxyanhydrides affords helical surface-tethered polymer chains that do not show any changes in secondary structure between 10 and 70 °C. QCM-D experiments, however, revealed significant dehydration of poly(γ-(2-(2-methoxyethoxy)ethyl)-l-glutamate) (poly(L-EG 2-Glu)) brushes upon heating from 10 to 40 °C. At the same time, AFM and ellipsometry studies did not reveal significant variations in film thickness over this temperature range, which is consistent with the shape-persistent nature of these polypeptide brushes and indicates that the thermoresponsiveness of the films is primarily due to hydration and dehydration of the oligo(ethylene glycol) side chains. The results we present here illustrate the potential of surface-initiated NCA ring-opening polymerization to generate densely grafted assemblies of polymer chains that possess well-defined secondary structures and tunable surface properties. These polypeptide brushes complement their conformationally unordered counterparts that can be generated via surface-initiated polymerization of vinyl-type monomers and represent another step forward to biomimetic surfaces and interfaces.« less

Weak polyelectrolyte complexation driven by associative charging.

PubMed

Rathee, Vikramjit S; Zervoudakis, Aristotle J; Sidky, Hythem; Sikora, Benjamin J; Whitmer, Jonathan K

2018-03-21

Weak polyelectrolytes are relevant for a wide range of fields; in particular, they have been investigated as "smart" materials for chemical separations and drug delivery. The charges on weak polyelectrolytes are dynamic, causing polymer chains to adopt different equilibrium conformations even with relatively small changes to the surrounding environment. Currently, there exists no comprehensive picture of this behavior, particularly where polymer-polymer interactions have the potential to affect charging properties significantly. In this study, we elucidate the novel interplay between weak polyelectrolyte charging and complexation behavior through coupled molecular dynamics and Monte Carlo simulations. Specifically, we investigate a model of two equal-length and oppositely charging polymer chains in an implicit salt solution represented through Debye-Hückel interactions. The charging tendency of each chain, along with the salt concentration, is varied to determine the existence and extent of cooperativity in charging and complexation. Strong cooperation in the charging of these chains is observed at large Debye lengths, corresponding to low salt concentrations, while at lower Debye lengths (higher salt concentrations), the chains behave in apparent isolation. When the electrostatic coupling is long-ranged, we find that a highly charged chain strongly promotes the charging of its partner chain, even if the environment is unfavorable for an isolated version of that partner chain. Evidence of this phenomenon is supported by a drop in the potential energy of the system, which does not occur at the lower Debye lengths where both potential energies and charge fractions converge for all partner chain charging tendencies. The discovery of this cooperation will be helpful in developing "smart" drug delivery mechanisms by allowing for better predictions for the dissociation point of delivery complexes.

Weak polyelectrolyte complexation driven by associative charging

NASA Astrophysics Data System (ADS)

Rathee, Vikramjit S.; Zervoudakis, Aristotle J.; Sidky, Hythem; Sikora, Benjamin J.; Whitmer, Jonathan K.

2018-03-01

Weak polyelectrolytes are relevant for a wide range of fields; in particular, they have been investigated as "smart" materials for chemical separations and drug delivery. The charges on weak polyelectrolytes are dynamic, causing polymer chains to adopt different equilibrium conformations even with relatively small changes to the surrounding environment. Currently, there exists no comprehensive picture of this behavior, particularly where polymer-polymer interactions have the potential to affect charging properties significantly. In this study, we elucidate the novel interplay between weak polyelectrolyte charging and complexation behavior through coupled molecular dynamics and Monte Carlo simulations. Specifically, we investigate a model of two equal-length and oppositely charging polymer chains in an implicit salt solution represented through Debye-Hückel interactions. The charging tendency of each chain, along with the salt concentration, is varied to determine the existence and extent of cooperativity in charging and complexation. Strong cooperation in the charging of these chains is observed at large Debye lengths, corresponding to low salt concentrations, while at lower Debye lengths (higher salt concentrations), the chains behave in apparent isolation. When the electrostatic coupling is long-ranged, we find that a highly charged chain strongly promotes the charging of its partner chain, even if the environment is unfavorable for an isolated version of that partner chain. Evidence of this phenomenon is supported by a drop in the potential energy of the system, which does not occur at the lower Debye lengths where both potential energies and charge fractions converge for all partner chain charging tendencies. The discovery of this cooperation will be helpful in developing "smart" drug delivery mechanisms by allowing for better predictions for the dissociation point of delivery complexes.

DNA Packaging in Bacteriophage: Is Twist Important?

PubMed Central

Spakowitz, Andrew James; Wang, Zhen-Gang

2005-01-01

We study the packaging of DNA into a bacteriophage capsid using computer simulation, specifically focusing on the potential impact of twist on the final packaged conformation. We perform two dynamic simulations of packaging a polymer chain into a spherical confinement: one where the chain end is rotated as it is fed, and one where the chain is fed without end rotation. The final packaged conformation exhibits distinct differences in these two cases: the packaged conformation from feeding with rotation exhibits a spool-like character that is consistent with experimental and previous theoretical work, whereas feeding without rotation results in a folded conformation inconsistent with a spool conformation. The chain segment density shows a layered structure, which is more pronounced for packaging with rotation. However, in both cases, the conformation is marked by frequent jumps of the polymer chain from layer to layer, potentially influencing the ability to disentangle during subsequent ejection. Ejection simulations with and without Brownian forces show that Brownian forces are necessary to achieve complete ejection of the polymer chain in the absence of external forces. PMID:15805174

DNA packaging in bacteriophage: is twist important?

PubMed

Spakowitz, Andrew James; Wang, Zhen-Gang

2005-06-01

We study the packaging of DNA into a bacteriophage capsid using computer simulation, specifically focusing on the potential impact of twist on the final packaged conformation. We perform two dynamic simulations of packaging a polymer chain into a spherical confinement: one where the chain end is rotated as it is fed, and one where the chain is fed without end rotation. The final packaged conformation exhibits distinct differences in these two cases: the packaged conformation from feeding with rotation exhibits a spool-like character that is consistent with experimental and previous theoretical work, whereas feeding without rotation results in a folded conformation inconsistent with a spool conformation. The chain segment density shows a layered structure, which is more pronounced for packaging with rotation. However, in both cases, the conformation is marked by frequent jumps of the polymer chain from layer to layer, potentially influencing the ability to disentangle during subsequent ejection. Ejection simulations with and without Brownian forces show that Brownian forces are necessary to achieve complete ejection of the polymer chain in the absence of external forces.

Miscibility phase diagram of ring-polymer blends: A topological effect.

PubMed

Sakaue, Takahiro; Nakajima, Chihiro H

2016-04-01

The miscibility of polymer blends, a classical problem in polymer science, may be altered, if one or both of the component do not have chain ends. Based on the idea of topological volume, we propose a mean-field theory to clarify how the topological constraints in ring polymers affect the phase behavior of the blends. While the large enhancement of the miscibility is expected for ring-linear polymer blends, the opposite trend toward demixing, albeit comparatively weak, is predicted for ring-ring polymer blends. Scaling formulas for the shift of critical point for both cases are derived. We discuss the valid range of the present theory, and the crossover to the linear polymer blends behaviors, which is expected for short chains. These analyses put forward a view that the topological constraints could be represented as an effective excluded-volume effects, in which the topological length plays a role of the screening factor.

Interfacial properties of hydrosoluble polymers. Final report, June 15, 1993--June 15, 1996

DOE Office of Scientific and Technical Information (OSTI.GOV)

NONE

1996-12-31

During this period, the authors treated a myriad of problems associated with the interfacial properties of macromolecules. Many of them concerned indirect interactions between surfaces engendered by intervening species. The issues ranged from colloidal forces to membrane induced coupling between embedded macromolecules (membrane-bound proteins). This report presents summaries of the following papers published as a result of this study: membrane interactions with polymers and colloids; escape transitions and force laws for compressed polymer mushrooms; interaction between finite-sized particles and end grafted polymers; one long chain among shorter chains--the Flory approach revisited; conformation of star polymers in high molecular weight solvents;more » membrane-induced interactions between inclusions; filled polymer brushes--a hydrodynamic analogy; polymer adsorption at liquid/air interfaces under lateral pressure; flow induced instability of the interface between a fluid and a gel at low Reynolds number; and fluctuation-induced forces in stacked fluid membranes.« less

The effect of side-chain substitution and hot processing on diketopyrrolopyrrole-based polymers for organic solar cells.

PubMed

Heintges, Gaël H L; Leenaers, Pieter J; Janssen, René A J

2017-07-14

The effects of cold and hot processing on the performance of polymer-fullerene solar cells are investigated for diketopyrrolopyrrole (DPP) based polymers that were specifically designed and synthesized to exhibit a strong temperature-dependent aggregation in solution. The polymers, consisting of alternating DPP and oligothiophene units, are substituted with linear and second position branched alkyl side chains. For the polymer-fullerene blends that can be processed at room temperature, hot processing does not enhance the power conversion efficiencies compared to cold processing because the increased solubility at elevated temperatures results in the formation of wider polymer fibres that reduce charge generation. Instead, hot processing seems to be advantageous when cold processing is not possible due to a limited solubility at room temperature. The resulting morphologies are consistent with a nucleation-growth mechanism for polymer fibres during drying of the films.

Dissipative particle dynamics simulations of polymer chains: scaling laws and shearing response compared to DNA experiments.

PubMed

Symeonidis, Vasileios; Em Karniadakis, George; Caswell, Bruce

2005-08-12

Dissipative particle dynamics simulations of several bead-spring representations of polymer chains in dilute solution are used to demonstrate the correct static scaling laws for the radius of gyration. Shear flow results for the wormlike chain simulating single DNA molecules compare well with average extensions from experiments, irrespective of the number of beads. However, coarse graining with more than a few beads degrades the agreement of the autocorrelation of the extension.

Controlled chain polymerisation and chemical soldering for single-molecule electronics.

PubMed

Okawa, Yuji; Akai-Kasaya, Megumi; Kuwahara, Yuji; Mandal, Swapan K; Aono, Masakazu

2012-05-21

Single functional molecules offer great potential for the development of novel nanoelectronic devices with capabilities beyond today's silicon-based devices. To realise single-molecule electronics, the development of a viable method for connecting functional molecules to each other using single conductive polymer chains is required. The method of initiating chain polymerisation using the tip of a scanning tunnelling microscope (STM) is very useful for fabricating single conductive polymer chains at designated positions and thereby wiring single molecules. In this feature article, developments in the controlled chain polymerisation of diacetylene compounds and the properties of polydiacetylene chains are summarised. Recent studies of "chemical soldering", a technique enabling the covalent connection of single polydiacetylene chains to single functional molecules, are also introduced. This represents a key step in advancing the development of single-molecule electronics.

Molecular dynamics simulation aiming at interfacial characteristics of polymer chains on nanotubes with different layers

NASA Astrophysics Data System (ADS)

Li, Kun; Gu, Boqin; Zhu, Wanfu

2017-03-01

A molecular dynamics (MD) simulations study is performed on multiwalled carbon nanotubes (MWNTs)/acrylonitrile-butadiene rubber (NBR) composites. The physisorption and interfacial characteristics between the various MWNTs and polymer macromolecular chains are identified. The effects of nanotube layers on the nanotubes/polymer interactions are examined. Each of the situation result and surface features is characterized by binding energy (Eb). It is shown that the binding energy (Eb) increase with the number of layers.

Non-immunogenic, hydrophilic/cationic block copolymers and uses thereof

DOEpatents

Scales, Charles W.; Huang, Faqing; McCormick, Charles L.

2010-05-18

The present invention provides novel non-immunogenic, hydrophilic/cationic block copolymers comprising a neutral-hydrophilic polymer and a cationic polymer, wherein both polymers have well-defined chain-end functionality. A representative example of such a block copolymer comprises poly(N-(2-hydroxypropyl)methacrylamide) (PHPMA) and poly(N-[3-(dimethylamino)propyl]methacrylamide) (PDMAPMA). Also provided is a synthesis method thereof in aqueous media via reversible addition fragmentation chain transfer (RAFT) polymerization. Further provided are uses of these block copolymers as drug delivery vehicles and protection agents.

Analog modeling of Worm-Like Chain molecules using macroscopic beads-on-a-string.

PubMed

Tricard, Simon; Feinstein, Efraim; Shepherd, Robert F; Reches, Meital; Snyder, Phillip W; Bandarage, Dileni C; Prentiss, Mara; Whitesides, George M

2012-07-07

This paper describes an empirical model of polymer dynamics, based on the agitation of millimeter-sized polymeric beads. Although the interactions between the particles in the macroscopic model and those between the monomers of molecular-scale polymers are fundamentally different, both systems follow the Worm-Like Chain theory.

Chain dynamics and nanoparticle motion in attractive polymer nanocomposites subjected to large deformations.

PubMed

Senses, Erkan; Tyagi, Madhusudan; Natarajan, Bharath; Narayanan, Suresh; Faraone, Antonio

2017-11-08

The effect of large deformation on the chain dynamics in attractive polymer nanocomposites was investigated using neutron scattering techniques. Quasi-elastic neutron backscattering measurements reveal a substantial reduction of polymer mobility in the presence of attractive, well-dispersed nanoparticles. In addition, large deformations are observed to cause a further slowing down of the Rouse rates at high particle loadings, where the interparticle spacings are slightly smaller than the chain dimensions, i.e. in the strongly confined state. No noticeable change, however, was observed for a lightly confined system. The reptation tube diameter, measured by neutron spin echo, remained unchanged after shear, suggesting that the level of chain-chain entanglements is not significantly affected. The shear-induced changes in the interparticle bridging reflect the slow nanoparticle motion measured by X-ray photon correlation spectroscopy. These results provide a first step for understanding how large shear can significantly affect the segmental motion in nanocomposites and open up new opportunities for designing mechanically responsive soft materials.

Chain dynamics and nanoparticle motion in attractive polymer nanocomposites subjected to large deformations

DOE PAGES

Senses, Erkan; Tyagi, Madhusudan; Natarajan, Bharath; ...

2017-09-28

The effect of large deformation on the chain dynamics in attractive polymer nanocomposites was investigated using neutron scattering techniques. Quasielastic neutron backscattering measurements reveal a substantial reduction of polymer mobility in the presence of attractive, well-dispersed nanoparticles. Additionally, large deformations are observed to cause a further slowing down of the Rouse rates at high particle loadings, where the interparticle spacings are slightly smaller than the chain dimensions, i.e. in the strongly confined state. No noticeable change, however, was observed for a lightly confined system. The reptation tube diameter, measured by neutron spin echo, remained unchanged after shear, suggesting that themore » level of chain-chain entanglements is not significantly affected. The shearinduced changes in the interparticle bridging reflects on the slow nanoparticle motion measured by X-ray photon correlation spectroscopy. These results provide a first step for understanding how large shear can significantly affect the segmental motion in nanocomposites and open up new opportunities for designing mechanically responsive soft materials.« less

Chain dynamics and nanoparticle motion in attractive polymer nanocomposites subjected to large deformations

DOE Office of Scientific and Technical Information (OSTI.GOV)

Senses, Erkan; Tyagi, Madhusudan; Natarajan, Bharath

The effect of large deformation on the chain dynamics in attractive polymer nanocomposites was investigated using neutron scattering techniques. Quasielastic neutron backscattering measurements reveal a substantial reduction of polymer mobility in the presence of attractive, well-dispersed nanoparticles. Additionally, large deformations are observed to cause a further slowing down of the Rouse rates at high particle loadings, where the interparticle spacings are slightly smaller than the chain dimensions, i.e. in the strongly confined state. No noticeable change, however, was observed for a lightly confined system. The reptation tube diameter, measured by neutron spin echo, remained unchanged after shear, suggesting that themore » level of chain-chain entanglements is not significantly affected. The shearinduced changes in the interparticle bridging reflects on the slow nanoparticle motion measured by X-ray photon correlation spectroscopy. These results provide a first step for understanding how large shear can significantly affect the segmental motion in nanocomposites and open up new opportunities for designing mechanically responsive soft materials.« less

Collective effects on activated segmental relaxation in supercooled polymer melts

NASA Astrophysics Data System (ADS)

Mirigian, Stephen; Schweizer, Kenneth

2013-03-01

We extend the polymer nonlinear Langevin equation (NLE) theory of activated segmental dynamics in supercooled polymer melts in two new directions. First, a well-defined mapping from real monomers to a freely-jointed chain is formulated that retains information about chain stiffness, monomer volume, and the amplitude of thermal density fluctuations. Second, collective effects beyond the local cage scale are included based on an elastic solid-state perspective in the ``shoving model'' spirit which accounts for longer range contributions to the activation barrier. In contrast to previous phenomenological treatments of this model, we formulate an explicit microscopic picture of the hopping event, and derive, not assume, that the collective barrier is directly related to the elastic shear modulus. Local hopping is thus renormalized by collective motions of the surroundings that are required to physically accommodate it. Using the PRISM theory of structure, and known compressibility and chain statistics information, quantitative applications of the new theory to predict the temperature and chain length dependence of the alpha time, shear modulus, and fragility are carried out for a range of real polymer liquids and compared to experiment.

Method for promoting specific alignment of short oligonucleotides on nucleic acids

DOEpatents

Studier, F. William; Kieleczawa, Jan; Dunn, John J.

1996-01-01

Disclosed is a method for promoting specific alignment of short oligonucleotides on a nucleic acid polymer. The nucleic acid polymer is incubated in a solution containing a single-stranded DNA-binding protein and a plurality of oligonucleotides which are perfectly complementary to distinct but adjacent regions of a predetermined contiguous nucleotide sequence in the nucleic acid polymer. The plurality of oligonucleotides anneal to the nucleic acid polymer to form a contiguous region of double stranded nucleic acid. Specific application of the methods disclosed include priming DNA synthesis and template-directed ligation.

Nanoparticle amount, and not size, determines chain alignment and nonlinear hardening in polymer nanocomposites

PubMed Central

Varol, H. Samet; Meng, Fanlong; Hosseinkhani, Babak; Malm, Christian; Bonn, Daniel; Bonn, Mischa; Zaccone, Alessio

2017-01-01

Polymer nanocomposites—materials in which a polymer matrix is blended with nanoparticles (or fillers)—strengthen under sufficiently large strains. Such strain hardening is critical to their function, especially for materials that bear large cyclic loads such as car tires or bearing sealants. Although the reinforcement (i.e., the increase in the linear elasticity) by the addition of filler particles is phenomenologically understood, considerably less is known about strain hardening (the nonlinear elasticity). Here, we elucidate the molecular origin of strain hardening using uniaxial tensile loading, microspectroscopy of polymer chain alignment, and theory. The strain-hardening behavior and chain alignment are found to depend on the volume fraction, but not on the size of nanofillers. This contrasts with reinforcement, which depends on both volume fraction and size of nanofillers, potentially allowing linear and nonlinear elasticity of nanocomposites to be tuned independently. PMID:28377517

End-Functionalized Palladium SCS Pincer Polymers via Controlled Radical Polymerizations.

PubMed

Lye, Diane S; Cohen, Aaron E; Wong, Madeleine Z; Weck, Marcus

2017-07-01

A direct and facile route toward semitelechelic polymers, end-functionalized with palladated sulfur-carbon-sulfur pincer (Pd II -pincer) complexes is reported that avoids any post-polymerization step. Key to our methodology is the combination of reversible addition-fragmentation chain-transfer (RAFT) polymerization with functionalized chain-transfer agents. This strategy yields Pd end-group-functionalized materials with monomodal molar mass dispersities (Đ) of 1.18-1.44. The RAFT polymerization is investigated using a Pd II -pincer chain-transfer agent for three classes of monomers: styrene, tert-butyl acrylate, and N-isopropylacrylamide. The ensuing Pd II -pincer end-functionalized polymers are analyzed using 1 H NMR spectroscopy, gel-permeation chromatography, and elemental analysis. The RAFT polymerization methodology provides a direct pathway for the fabrication of Pd II -pincer functionalized polymers with complete end-group functionalization. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Evidence for a jacketed nematic polymer

NASA Astrophysics Data System (ADS)

Hardouin, F.; Mery, S.; Achard, M. F.; Noirez, L.; Keller, P.

1991-05-01

The evidence for a “jacketed” structure at the scale of the chain dimensions in the nematic phase of a “side-on fixed” liquid crystal polysiloxane is reported by using small angle neutron scattering. We relate this anisotropy of chain conformation to the first measurements of the rotational viscosity coefficient in this new type of liquid crystal side-chain polymer. Par des mesures de diffusion des neutrons aux petits angles nous montrons l'existence, pour un polysiloxane “ en haltère ”, d'une structure “ chemisée ” à l'échelle de l'organisation global d'une chaîne en phase nématique. On constate que cette anisotropie de forme du polymère a des conséquences sur l'évolution du coefficient de viscosité de torsion mesuré pour la première fois dans ce nouveau type de polymère à chaînes latérales.

Slide-Ring Materials Using Cyclodextrin.

PubMed

Ito, Kohzo

2017-01-01

We have recently synthesized slide-ring materials using cyclodextrin by cross-linking polyrotaxanes, a typical supramolecule. The slide-ring materials have polymer chains with bulky end groups topologically interlocked by figure-of-eight shaped junctions. This indicates that the cross-links can pass through the polymer chains similar to pulleys to relax the tension of the backbone polymer chains. The slide-ring materials also differ from conventional polymers in that the entropy of rings affects the elasticity. As a result, the slide-ring materials show quite small Young's modulus not proportional to the cross-linking density. This concept can be applied to a wide variety of polymeric materials as well as gels. In particular, the slide-ring materials show remarkable scratch-proof properties for coating materials for automobiles, cell phones, mobile computers, and so on. Further current applications include vibration-proof insulation materials for sound speakers, highly abrasive polishing media, dielectric actuators, and so on.

Analysis of self-oscillating behaviors aimed at the development of a molecular robot with organic acids as fuel

NASA Astrophysics Data System (ADS)

Nakazumi, Tomoka; Hara, Yusuke

2017-09-01

We studied the transmittance self-oscillation of a polymer chain driven by an organic acid as the fuel. The self-oscillating polymer chain consists of 4-acryloylmorpholine (ACMO) and the Ru catalyst (Ru(bpy)3) of the Belousov-Zhabotinsky (BZ) reaction. The transmittance self-oscillating behavior was affected significantly by the temperature. As the amplitude of the transmittance self-oscillation, which is reflected by the aggregation state, decreased with time, the oscillation period also decreased. This trend indicates that the polymer aggregation affects the rate of the BZ reaction significantly. The activation energy of the self-oscillating value was almost the same in the normal BZ reaction, which does not include Ru(bpy)3 complexes in the polymer chains. In addition, we demonstrated the effect of one BZ substrate (sodium bromate or malonic acid) on the transmittance self-oscillation period.

Playing with Polymers.

ERIC Educational Resources Information Center

Chemecology, 1997

1997-01-01

Presents an activity that enables students to gain a better understanding of the importance of polymers. Students perform an experiment in which polymer chains of polyvinyl acetate form crosslinks. Includes background information and discussion questions. (DDR)

Crystallization in melts of short, semiflexible hard polymer chains: An interplay of entropies and dimensions

NASA Astrophysics Data System (ADS)

Shakirov, T.; Paul, W.

2018-04-01

What is the thermodynamic driving force for the crystallization of melts of semiflexible polymers? We try to answer this question by employing stochastic approximation Monte Carlo simulations to obtain the complete thermodynamic equilibrium information for a melt of short, semiflexible polymer chains with purely repulsive nonbonded interactions. The thermodynamics is obtained based on the density of states of our coarse-grained model, which varies by up to 5600 orders of magnitude. We show that our polymer melt undergoes a first-order crystallization transition upon increasing the chain stiffness at fixed density. This crystallization can be understood by the interplay of the maximization of different entropy contributions in different spatial dimensions. At sufficient stiffness and density, the three-dimensional orientational interactions drive the orientational ordering transition, which is accompanied by a two-dimensional translational ordering transition in the plane perpendicular to the chains resulting in a hexagonal crystal structure. While the three-dimensional ordering can be understood in terms of Onsager theory, the two-dimensional transition can be understood in terms of the liquid-hexatic transition of hard disks. Due to the domination of lateral two-dimensional translational entropy over the one-dimensional translational entropy connected with columnar displacements, the chains form a lamellar phase. Based on this physical understanding, orientational ordering and translational ordering should be separable for polymer melts. A phenomenological theory based on this understanding predicts a qualitative phase diagram as a function of volume fraction and stiffness in good agreement with results from the literature.

Shifting of the melting point for semi-crystalline polymer nanofibers

NASA Astrophysics Data System (ADS)

Arinstein, A.; Liu, Y.; Rafailovich, M.; Zussman, E.

2011-02-01

The depression of melting temperature as a function of the diameter of electrospun semi-crystalline polymer nanofibers is discussed. Due to fast solvent evaporation during nanofiber electrospinning, there occurs the fixation of topological structure of the polymer matrix corresponding to chain entanglement of the initial concentration of the semi-dilute solution. The resulting level of chain entanglement is lower than that in polymer bulk at equilibrium. This difference results in an addition to the entropy jump corresponding to the polymer's melting, and accounts for the observed shift in melting temperature in as-spun fibers. The proposed concept is found to be in good agreement with experimental results obtained for as-spun poly(ethylene-co-vinyl acetate) (PEVA) and low-density polyethylene (LDPE) fibers.

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

PubMed

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

2017-09-27

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

Healing of polymer interfaces: Interfacial dynamics, entanglements, and strength

DOE PAGES

Ge, Ting; Robbins, Mark O.; Perahia, Dvora; ...

2014-07-25

Self-healing of polymer films often takes place as the molecules diffuse across a damaged region, above their melting temperature. Using molecular dynamics simulations we probe the healing of polymer films and compare the results with those obtained for thermal welding of homopolymer slabs. These two processes differ from each other in their interfacial structure since damage leads to increased polydispersity and more short chains. A polymer sample was cut into two separate films that were then held together in the melt state. The recovery of the damaged film was followed as time elapsed and polymer molecules diffused across the interface.more » The mass uptake and formation of entanglements, as obtained from primitive path analysis, are extracted and correlated with the interfacial strength obtained from shear simulations. We find that the diffusion across the interface is signifcantly faster in the damaged film compared to welding because of the presence of short chains. Though interfacial entanglements increase more rapidly for the damaged films, a large fraction of these entanglements are near chain ends. As a result, the interfacial strength of the healing film increases more slowly than for welding. For both healing and welding, the interfacial strength saturates as the bulk entanglement density is recovered across the interface. However, the saturation strength of the damaged film is below the bulk strength for the polymer sample. At saturation, cut chains remain near the healing interface. They are less entangled and as a result they mechanically weaken the interface. When the strength of the interface saturates, the number of interfacial entanglements scales with the corresponding bulk entanglement density. Chain stiffness increases the density of entanglements, which increases the strength of the interface. Our results show that a few entanglements across the interface are sufficient to resist interfacial chain pullout and enhance the mechanical strength.« less

Forced reptation revealed by chain pull-out simulations.

PubMed

Bulacu, Monica; van der Giessen, Erik

2009-08-14

We report computation results obtained from extensive molecular dynamics simulations of tensile disentanglement of connector chains placed at the interface between two polymer bulks. Each polymer chain (either belonging to the bulks or being a connector) is treated as a sequence of beads interconnected by springs, using a coarse-grained representation based on the Kremer-Grest model, extended to account for stiffness along the chain backbone. Forced reptation of the connectors was observed during their disentanglement from the bulk chains. The extracted chains are clearly seen following an imaginary "tube" inside the bulks as they are pulled out. The entropic and energetic responses to the external deformation are investigated by monitoring the connector conformation tensor and the modifications of the internal parameters (bonds, bending, and torsion angles along the connectors). The work needed to separate the two bulks is computed from the tensile force induced during debonding in the connector chains. The value of the work reached at total separation is considered as the debonding energy G. The most important parameters controlling G are the length (n) of the chains placed at the interface and their areal density. Our in silico experiments are performed at relatively low areal density and are disregarded if chain scission occurs during disentanglement. As predicted by the reptation theory, for this pure pull-out regime, the power exponent from the scaling G proportional, variant n(a) is a approximately 2, irrespective of chain stiffness. Small variations are found when the connectors form different number of stitches at the interface, or when their length is randomly distributed in between the two bulks. Our results show that the effects of the number of stitches and of the randomness of the block lengths have to be considered together, especially when comparing with experiments where they cannot be controlled rigorously. These results may be significant for industrial applications, such reinforcement of polymer-polymer adhesion by connector chains, when incorporated as constitutive laws at higher time/length scales in finite element calculations.

Advanced Polymer Network Structures

DTIC Science & Technology

2016-02-01

double networks in a single step was identified from coarse-grained molecular dynamics simulations of polymer solvents bearing rigid side chains dissolved...in a polymer network. Coarse-grained molecular dynamics simulations also explored the mechanical behavior of traditional double networks and...DRI), polymer networks, polymer gels, molecular dynamics simulations , double networks 16. SECURITY CLASSIFICATION OF: 17. LIMITATION OF

Influence of the Location of Attractive Polymer-Pore Interactions on Translocation Dynamics.

PubMed

Ghosh, Bappa; Chaudhury, Srabanti

2018-01-11

We probe the influence of polymer-pore interactions on the translocation dynamics using Langevin dynamics simulations. We investigate the effect of the strength and location of the polymer-pore interaction using nanopores that are partially charged either at the entry or the exit or on both sides of the pore. We study the change in the translocation time as a function of the strength of the polymer-pore interaction for a given chain length and under the effect of an externally applied field. Under a moderate driving force and a chain length longer than the length of the pore, the translocation time shows a nonmonotonic increase with an increase in the attractive interaction. Also, an interaction on the cis side of the pore can increase the translocation probability. In the presence of an external field and a strong attractive force, the translocation time for shorter chains is independent of the polymer-pore interaction at the entry side of the pore, whereas an interaction on the trans side dominates the translocation process. Our simulation results are rationalized by a qualitative analysis of the free energy landscape for polymer translocation.

Synthetic and Biopolymer Gels - Similarities and Difference.

NASA Astrophysics Data System (ADS)

Horkay, Ferenc

2006-03-01

Ion exchange plays a central role in a variety of physiological processes, such as nerve excitation, muscle contraction and cell locomotion. Hydrogels can be used as model systems for identifying fundamental chemical and physical interactions that govern structure formation, phase transition, etc. in biopolymer systems. Polyelectrolyte gels are particularly well-suited to study ion-polymer interactions because their structure and physical-chemical properties (charge density, crosslink density, etc) can be carefully controlled. They are sensitive to different external stimuli such as temperature, ionic composition and pH. Surprisingly few investigations have been made on polyelectrolyte gels in salt solutions containing both monovalent and multivalent cations. We have developed an experimental approach that combines small angle neutron scattering and osmotic swelling pressure measurements. The osmotic pressure exerted on a macroscopic scale is a consequence of changes occurring at a molecular level. The intensity of the neutron scattering signal, which provides structural information as a function of spatial resolution, is directly related to the osmotic pressure. We have found a striking similarity in the scattering and osmotic behavior of polyacrylic acid gels and DNA gels swollen in nearly physiological salt solutions. Addition of calcium ions to both systems causes a sudden volume change. This volume transition, which occurs when the majority of the sodium counterions are replaced by calcium ions, is reversible. Such reversibility implies that the calcium ions are not strongly bound by the polyanion, but are free to move along the polymer chain, which allows these ions to form temporary bridges between negative charges on adjacent chains. Mechanical measurements reveal that the elastic modulus is practically unchanged in the calcium-containing gels, i.e., ion bridging is qualitatively different from covalent crosslinks.

Study of fracture and stress-induced morphological instabilities in polymeric materials

NASA Astrophysics Data System (ADS)

Sabouri-Ghomi, Mohsen

We study the phenomena of fracture in polymers at the molecular and continuum level. At a molecular level, we study the failure of polymer/polymer interfaces. Our main focus is on a specific mode of failure known as chain pull-out fracture, which is common to weak adhesive junctions, and polymer blends and mixtures. In the case of the interface between incompatible polymers, reinforcement is achieved by adding a block copolymer to the interface. We introduce a microscopic model based on Brownian dynamics to investigate the effect of the polymerization index N, of the block connector chain, on fracture toughness of such reinforced polymeric junctions. We consider the mushroom regime, where connector chains are grafted with low surface density, for the case of large pulling velocity. We find that for short chains the interface fracture toughness depends linearly on the polymerization index N of the connector chains, while for longer chains the dependence becomes N 3/2. We propose a scaling argument, based on the geometry of the initial configuration, that accounts for both short and long chains and the crossover between them. At the continuum level, we study the pattern selection mechanism of finger-like crack growth phenomena in gradient driven growth problems in general, and the structure of stress-induced morphological instabilities in crazing of polymer glasses in particular. We simulate solidification in a narrow channel through the use of a phase-field model with an adaptive grid. By tuning a dimensionless parameter, the Peclet number, we show a continuous crossover from a free dendrite at high Peclet numbers to anisotropic viscous fingering at low Peclet numbers. At low Peclet numbers we find good agreement between our results, theoretical predictions, and experiment, providing the first quantitative test of solvability theory for anisotropic viscous fingers. For high undercoolings, we find new phenomena, a solid forger which satisfies stability and thermodynamic criterion. We further provide an analytical form for the shape of these fingers, based on local models of solidification, which fits our numerical results from simulation. Later we study the growth of crazes in polymer glasses by deriving the equations of motion of plastic flow at the craze tip, and the steady-state velocity profile of this flow. By developing a phenomenological model, we solve the full time-dependent equations of motion of this highly non-linear phenomena. Our simulation produces the steady-state cellular pattern observed in experiments. We further show that polymer glasses with lower yield stress produce cellular patterns with sharper tips and more cells, indicating instabilities with smaller wavelengths.

On the Wrapping of Polyglycolide, Poly(Ethylene Oxide), and Polyketone Polymer Chains Around Single-Walled Carbon Nanotubes Using Molecular Dynamics Simulations

NASA Astrophysics Data System (ADS)

Rouhi, S.; Alizadeh, Y.; Ansari, R.

2015-02-01

By using molecular dynamics simulations, the interaction between a single-walled carbon nanotube and three different polymers has been studied in this work. The effects of various parameters such as the nanotube geometry and temperature on the interaction energy and radius of gyration of polymers have been explored. By studying the snapshots of polymers along the single-walled carbon nanotube, it has been shown that 50 ps can be considered as a suitable time after which the shape of polymer chains around the nanotube remains almost unchanged. It is revealed that the effect of temperature on the interaction energy and radius of gyration of polymers in the range of 250 to 500 K is not significant Also, it is shown that the interaction energy depends on the nanotube diameter.

Molecular Velcro constructed from polymer loop brushes showing enhanced adhesion force

NASA Astrophysics Data System (ADS)

Zhou, Tian; Han, Biao; Han, Lin; Li, Christopher; Department of Materials Science; Engineering Team; School of Biomedical Engineering, Science; Health Systems Team

2015-03-01

Molecular Velcro is commonly seen in biological systems as the formation of strong physical entanglement at molecular scale could induce strong adhesion, which is crucial to many biological processes. To mimic this structure, we designed, and fabricated polymer loop brushes using polymer single crystals with desired surface functionality and controlled chain folding. Compared with reported loop brushes fabricated using triblock copolymers, the present loop bushes have precise loop sizes, loop grafting density, and well controlled tethering locations on the solid surface. Atomic force microscopy-based force spectroscopy measurements using a polymer chain coated probe reveal that the adhesion force are significantly enhanced on the loop brush surface as compared with its single-strand counterpart. This study directly shows the effect of polymer brush conformation on their properties, and suggests a promising strategy for advanced polymer surface design.

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

Smart polymers as surface modifiers for bioanalytical devices and biomaterials: theory and practice

NASA Astrophysics Data System (ADS)

Ivanov, A. E.; Zubov, V. P.

2016-06-01

Smart, or responsive polymers can reversibly change their state of aggregation, thus switching from water-soluble to insoluble state, in response to minor changes in temperature, pH or solvent composition. Grafting of these polymers to solid surfaces imparts the surfaces with controllable wettability and adsorption behaviour. The review summarizes the theoretical models and the results of physical measurements of the conformational transitions in grafted polymer chains and polymer brushes. Primary attention is paid to the grafting density and the length and spatial arrangement of grafted chains, the role of polystyrene, organosilane or alkanethiol sublayers and their effects on adsorption of proteins and adhesion of cells. The key applications of grafted smart polymers such as cell culture and tissue engineering, cell and protein separation, biosensing and targeted drug delivery are surveyed. The bibliography includes 174 references.

Single-Chain Folding of Synthetic Polymers: A Critical Update.

PubMed

Altintas, Ozcan; Barner-Kowollik, Christopher

2015-11-23

The current contribution serves as a critical update to a previous feature article from us (Macromol. Rapid Commun. 2012, 33, 958-971), and highlights the latest advances in the preparation of single chain polymeric nanoparticles and initial-yet promising-attempts towards mimicking the structure of natural biomacromolecules via single-chain folding of well-defined linear polymers via so-called single chain selective point folding and repeat unit folding. The contribution covers selected examples from the literature published up to ca. September 2015. Our aim is not to provide an exhaustive review but rather highlight a selection of new and exciting examples for single-chain folding based on advanced macromolecular precision chemistry. Initially, the discussion focuses on the synthesis and characterization of single-chain folded structures via selective point folding. The second part of the feature article addresses the folding of well-defined single-chain polymers by means of repeat unit folding. The current state of the art in the field of single-chain folding indicates that repeat unit folding-driven nanoparticle preparation is well-advanced, while initial encouraging steps towards building selective point folding systems have been taken. In addition, a summary of the-in our view-open key questions is provided that may guide future biomimetic design efforts. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Discrete-to-continuum simulation approach to polymer chain systems: Subdiffusion, segregation, and chain folding

NASA Astrophysics Data System (ADS)

Foo, Grace M.; Pandey, R. B.

1998-05-01

A discrete-to-continuum approach is introduced to study the static and dynamic properties of polymer chain systems with a bead-spring chain model in two dimensions. A finitely extensible nonlinear elastic potential is used for the bond between the consecutive beads with the Lennard-Jones (LJ) potential with smaller (Rc=21/6σ=0.95) and larger (Rc=2.5σ=2.1) values of the upper cutoff for the nonbonding interaction among the neighboring beads. We find that chains segregate at temperature T=1.0 with Rc=2.1 and remain desegregated with Rc=0.95. At low temperature (T=0.2), chains become folded, in a ribbonlike conformation, unlike random and self-avoiding walk conformations at T=1.0. The power-law dependence of the rms displacements of the center of mass (Rc.m.) of the chains and their center node (Rcn) with time are nonuniversal, with the range of exponents ν1~=0.45-0.25 and ν2~=0.30-0.10, respectively. Both radius of gyration (Rg) and average bond length () decrease on increasing the range of interaction (Rc), consistent with the extended state in good solvent to collapsed state in poor solvent description of the polymer chains. Analysis of the radial distribution function supports these observations.

Decoupling of ion conductivity from segmental dynamics in oligomeric ethylene oxide functionalized oxanorbornene dicarboximide homopolymers

DOE PAGES

Adams, Marisa; Richmond, Victoria; Smith, Douglas; ...

2017-03-24

Here, in order to design more effective solid polymer electrolytes, it is important to decouple ion conductivityfrom polymer segmental motion. To that end, novel polymers based on oxanorbornene dicarboximidemonomers with varying lengths of oligomeric ethylene oxide side chains have been synthesized usingring opening metathesis polymerization. These unique polymers have a fairly rigid and bulky backboneand were used to investigate the decoupling of ion motion from polymer segmental dynamics. Ionconductivity was measured using broadband dielectric spectroscopy for varying levels of added lithiumsalt. The conductivity data demonstrate six to seven orders of separation in timescale of ion conductivityfrom polymer segmental motion formore » polymers with shorter ethylene oxide side chains. However,commensurate changes in the glass transition temperatures T g reduce the effect of decoupling in ionconductivity and lead to lower conductivity at ambient conditions. These results suggest that both anincrease in decoupling and a reduction in T g might be required to develop solid polymer electrolytes withhigh ion conductivity at room temperature.« less

Efficient Homodifunctional Bimolecular Ring-Closure Method for Cyclic Polymers by Combining RAFT and Self-Accelerating Click Reaction.

PubMed

Qu, Lin; Sun, Peng; Wu, Ying; Zhang, Ke; Liu, Zhengping

2017-08-01

An efficient metal-free homodifunctional bimolecular ring-closure method is developed for the formation of cyclic polymers by combining reversible addition-fragmentation chain transfer (RAFT) polymerization and self-accelerating click reaction. In this approach, α,ω-homodifunctional linear polymers with azide terminals are prepared by RAFT polymerization and postmodification of polymer chain end groups. By virtue of sym-dibenzo-1,5-cyclooctadiene-3,7-diyne (DBA) as small linkers, well-defined cyclic polymers are then prepared using the self-accelerating double strain-promoted azide-alkyne click (DSPAAC) reaction to ring-close the azide end-functionalized homodifunctional linear polymer precursors. Due to the self-accelerating property of DSPAAC ring-closing reaction, this novel method eliminates the requirement of equimolar amounts of telechelic polymers and small linkers in traditional bimolecular ring-closure methods. It facilitates this method to efficiently and conveniently produce varied pure cyclic polymers by employing an excess molar amount of DBA small linkers. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Angle-Dependent Atomic Force Microscopy Single-Chain Pulling of Adsorbed Macromolecules from Planar Surfaces Unveils the Signature of an Adsorption-Desorption Transition.

PubMed

Grebíková, Lucie; Whittington, Stuart G; Vancso, Julius G

2018-05-23

The adsorption-desorption behavior of polymer chains is at the heart of macromolecular surface science and technology. With the current developments in atomic force microscopy (AFM), it has now become possible to address the desorption problem from the perspective of a single macromolecule. Here, we report on desorption of single polymer chains on planar surfaces by AFM-based single molecule force spectroscopy (SMFS) as a function of the pulling angle with respect to the surface-normal direction. SMFS experiments were performed in water with various substrates using different polymers covalently attached to the AFM probe tip. End-grafting at the AFM tip was achieved by surface-initiated polymerization using initiator functionalized tips. We found that the desorption force increases with a decreasing pulling angle, i.e., an enhanced adhesion of the polymer chain was observed. The magnitude of the desorption force shows a weak angular dependence at pulling angles close to the surface normal. A significant increase of the force is observed at shallower pulling from a certain pulling angle. This behavior carries the signature of an adsorption-desorption transition. The angular dependence of the normalized desorption force exhibits a universal behavior. We compared and interpreted our results using theoretical predictions for single-chain adsorption-desorption transitions.

Angle-Dependent Atomic Force Microscopy Single-Chain Pulling of Adsorbed Macromolecules from Planar Surfaces Unveils the Signature of an Adsorption–Desorption Transition

PubMed Central

2018-01-01

The adsorption–desorption behavior of polymer chains is at the heart of macromolecular surface science and technology. With the current developments in atomic force microscopy (AFM), it has now become possible to address the desorption problem from the perspective of a single macromolecule. Here, we report on desorption of single polymer chains on planar surfaces by AFM-based single molecule force spectroscopy (SMFS) as a function of the pulling angle with respect to the surface-normal direction. SMFS experiments were performed in water with various substrates using different polymers covalently attached to the AFM probe tip. End-grafting at the AFM tip was achieved by surface-initiated polymerization using initiator functionalized tips. We found that the desorption force increases with a decreasing pulling angle, i.e., an enhanced adhesion of the polymer chain was observed. The magnitude of the desorption force shows a weak angular dependence at pulling angles close to the surface normal. A significant increase of the force is observed at shallower pulling from a certain pulling angle. This behavior carries the signature of an adsorption–desorption transition. The angular dependence of the normalized desorption force exhibits a universal behavior. We compared and interpreted our results using theoretical predictions for single-chain adsorption–desorption transitions. PMID:29712430

Degradation mechanism of polysaccharides on irradiated sugarcane bagasse

NASA Astrophysics Data System (ADS)

Ribeiro, M. A.; Oikawa, H.; Mori, M. N.; Napolitano, C. M.; Duarte, C. L.

2013-03-01

Sugarcane bagasse is composed of cellulose, hemicelluloses, lignin, and a minor amount of protein and inorganic materials. Cellulose consists of linear macromolecular chains of glucose, linked by β-1,4-glucosidic bonds between the number one and the number four carbon atoms of the adjacent glucose units. Hemicelluloses are heterogeneous polymers, unlike cellulose, and are usually composed of 50-200 monomer units of pentose such as xylose and arabinose. Lignin is a complex polymer of p-hydroxyphenylpropanoid units connected by CC and COC links. Radiation-induced reactions in the macromolecules of the cellulose materials are known to be initiated through fast distribution of the absorbed energy within the molecules to produce long- and short-lived radicals. The present study was carried out using sugarcane bagasse samples irradiated by a Radiation Dynamics electron beam accelerator with 1.5 MeV and 37 kW, with the objective to evaluate the cleavage of the polysaccharides and the by-products formed as a result of the absorbed dose. The electron beam processing in 30 kGy of absorbed dose changed the sugarcane bagasse structure and composition, causing some cellulose and hemicelluloses cleavage. These cleavages were partial, forming oligosaccharides and liberating the sugars glucose and arabinose. The main by-product was acetic acid, originated from the de-acetylating of hemicelluloses.

Theory and Simulation of Attractive Nanoparticle Transport in Polymer Melts

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yamamoto, Umi; Carrillo, Jan-Michael Y.; Bocharova, Vera

We theoretically study the diffusion of a single attractive nanoparticle (NP) in unentangled and entangled polymer melts based on combining microscopic “core–shell” and “vehicle” mechanisms in a dynamic bond percolation theory framework. A physical picture is constructed which addresses the role of chain length (N), degree of entanglement, nanoparticle size, and NP–polymer attraction strength. The nanoparticle diffusion constant is predicted to initially decrease with N due to the dominance of the core–shell mechanism, then to cross over to the vehicle diffusion regime with a weaker N dependence, and eventually plateau at large enough N. This behavior corresponds to decoupling ofmore » NP diffusivity from the macroscopic melt viscosity, which is reminiscent of repulsive NPs in entangled melts, but here it occurs for a distinct physical reason. Specifically, it reflects a crossover to a transport mechanism whereby nanoparticles adsorb on polymer chains and diffuse using them as “vehicles” over a characteristic desorption time scale. Repetition of random desorption events then leads to Fickian long time NP diffusion. Complementary simulations for a range of chain lengths and low to moderate NP–polymer attraction strengths are also performed. They allow testing of the proposed diffusion mechanisms and qualitatively support the theoretically predicted dynamic crossover behavior. In conclusion, when the desorption time is smaller than or comparable to the onset of entangled polymer dynamics, the NP diffusivity becomes almost chain length independent.« less

Theory and Simulation of Attractive Nanoparticle Transport in Polymer Melts

DOE PAGES

Yamamoto, Umi; Carrillo, Jan-Michael Y.; Bocharova, Vera; ...

2018-03-06

We theoretically study the diffusion of a single attractive nanoparticle (NP) in unentangled and entangled polymer melts based on combining microscopic “core–shell” and “vehicle” mechanisms in a dynamic bond percolation theory framework. A physical picture is constructed which addresses the role of chain length (N), degree of entanglement, nanoparticle size, and NP–polymer attraction strength. The nanoparticle diffusion constant is predicted to initially decrease with N due to the dominance of the core–shell mechanism, then to cross over to the vehicle diffusion regime with a weaker N dependence, and eventually plateau at large enough N. This behavior corresponds to decoupling ofmore » NP diffusivity from the macroscopic melt viscosity, which is reminiscent of repulsive NPs in entangled melts, but here it occurs for a distinct physical reason. Specifically, it reflects a crossover to a transport mechanism whereby nanoparticles adsorb on polymer chains and diffuse using them as “vehicles” over a characteristic desorption time scale. Repetition of random desorption events then leads to Fickian long time NP diffusion. Complementary simulations for a range of chain lengths and low to moderate NP–polymer attraction strengths are also performed. They allow testing of the proposed diffusion mechanisms and qualitatively support the theoretically predicted dynamic crossover behavior. In conclusion, when the desorption time is smaller than or comparable to the onset of entangled polymer dynamics, the NP diffusivity becomes almost chain length independent.« less

Optically detected magnetic resonance studies on pi-conjugated polymers and novel carbon allotropes

NASA Astrophysics Data System (ADS)

Partee, Jonathan Farel

1997-12-01

The photophysics of poly(p-phenylene)-type ladder polymers (m-LPPP) and 2,5-dibutoxy poly(p-phenylene ethynylene) (DBO-PPE) films and solutions were studied by X-band photoluminescence detected magnetic resonance (PLDMR). Frequency resolved PLDMR measurements on LPPP, DBO-PPE, poly(3-hexylthiophene) (P3HT), poly(p-phenylene-vinylene) (PPV), and Csb{70} are also reported and discussed. All the polymer samples exhibit three distinct features when excited at wavelengths lambda≥ 458nm: (i) A narrow PL-enhancing spin-1/2 polaron resonance, (ii) broad full- and (iii) half-field spin-1 triplet exciton powder patterns due to the Deltamsbs = 1 and Deltamsbs = 2 transitions among the triplet sublevels, respectively. The full-width at half maximum (FWHM) of the spin-1/2 resonance in LPPP decreased from film to solution. However, the FWHM of that resonance in PPE was identical at all concentrations. This spin-1/2 resonance is assigned to the magnetic resonance enhancement of the recombination of both interchain and intrachain-intersegment polaron pairs which quench singlet exciton recombination. In solid m-LPPP samples, the aggregate PL gives rise to a proportionally higher magnetic resonance effect than other parts of the PL spectrum. In DBO-PPE and m-LPPP solutions, the triplet resonance decreased with decreasing concentration. This suggests that the triplet state is an intrinsic long-lived (˜30mus) trapped state localized on a phenylene ring and stabilized by coupling to a unit of an adjacent chain. Frequency resolved measurements of the lifetime of the species affected by the resonance conditions for all the polymers are described and discussed. The lifetimes appeared to include: (i) fast (9mus ≤ tausb1 ≤ 40mus) and (ii) slow (575mus\\ ≤ tausb2≤ 1868mus) components. The lifetimes increased with increasing concentration of the polymers in toluene solutions. These results can be interpreted to provide support for the interchain/intersegment polaron model or a distribution of lifetimes model.

Side-chain Liquid Crystal Polymers (SCLCP): Methods and Materials. An Overview

PubMed Central

Ganicz, Tomasz; Stańczyk, Włodzimierz

2009-01-01

This review focuses on recent developments in the chemistry of side chain liquid crystal polymers. It concentrates on current trends in synthetic methods and novel, well defined structures, supramolecular arrangements, properties, and applications. The review covers literature published in this century, apart from some areas, such as dendritic and elastomeric systems, which have been recently reviewed.

Chain conformations dictate multiscale charge transport phenomena in disordered semiconducting polymers

PubMed Central

Noriega, Rodrigo; Salleo, Alberto; Spakowitz, Andrew J.

2013-01-01

Existing models for the electronic properties of conjugated polymers do not capture the spatial arrangement of the disordered macromolecular chains over which charge transport occurs. Here, we present an analytical and computational description in which the morphology of individual polymer chains is dictated by well-known statistical models and the electronic coupling between units is determined using Marcus theory. The multiscale transport of charges in these materials (high mobility at short length scales, low mobility at long length scales) is naturally described with our framework. Additionally, the dependence of mobility with electric field and temperature is explained in terms of conformational variability and spatial correlation. Our model offers a predictive approach to connecting processing conditions with transport behavior. PMID:24062459

Chain conformations dictate multiscale charge transport phenomena in disordered semiconducting polymers.

PubMed

Noriega, Rodrigo; Salleo, Alberto; Spakowitz, Andrew J

2013-10-08

Existing models for the electronic properties of conjugated polymers do not capture the spatial arrangement of the disordered macromolecular chains over which charge transport occurs. Here, we present an analytical and computational description in which the morphology of individual polymer chains is dictated by well-known statistical models and the electronic coupling between units is determined using Marcus theory. The multiscale transport of charges in these materials (high mobility at short length scales, low mobility at long length scales) is naturally described with our framework. Additionally, the dependence of mobility with electric field and temperature is explained in terms of conformational variability and spatial correlation. Our model offers a predictive approach to connecting processing conditions with transport behavior.

Polymers Are Everywhere.

ERIC Educational Resources Information Center

Seymour, Raymond B.

1988-01-01

Describes the history of the human understanding of polymers from alchemy to modern times. Discusses renaissance chemistry, polymers in the nineteenth century, synthetic elastomers, thermoplastic elastomers, fibers, coatings, adhesives, derivatives of natural rubber, thermosets, step-reaction, and chain polymerization. (CW)

Dynamical behavior of a single polymer chain under nanometric confinement

NASA Astrophysics Data System (ADS)

Lagrené, K.; Zanotti, J.-M.; Daoud, M.; Farago, B.; Judeinstein, P.

2010-10-01

We address the dynamical behavior of a single polymer chain under nanometric confinement. We consider a polymer melt made of a mixture of hydrogenated and deuterated high molecular mass Poly(Ethylene Oxide) (PEO). The confining material is a membrane of Anodic Aluminum Oxide (AAO), a macroscopically highly ordered confining system made of parallel cylindrical channels. We use Neutron Spin-Echo (NSE) under the Zero Average Contrast (ZAC) condition to, all at once, i) match the intense porous AAO detrimental elastic SANS (Small Angle Neutron Scattering) contribution to the total intermediate scattering function I(Q,t) and ii) measure the Q dependence of the dynamical modes of a single chain under confinement. The polymer dynamics is probed on an extremely broad spacial ([2.2 10-2 Å-1, 0.2 Å-1]) and temporal ([0.1 ns, 600 ns]) ranges. We do not detect any influence of confinement on the polymer dynamics. This result is discussed in the framework of the debate on the existence of a "corset effect" recently suggested by NMR relaxometry data.

Dynamic Scaling Theory of the Forced Translocation of a Semi-flexible Polymer Through a Nanopore

NASA Astrophysics Data System (ADS)

Lam, Pui-Man; Zhen, Yi

2015-10-01

We present a theoretical description of the dynamics of a semi-flexible polymer being pulled through a nanopore by an external force acting at the pore. Our theory is based on the tensile blob picture of Pincus in which the front of the tensile force propagates through the backbone of the polymer, as suggested by Sakaue and recently applied to study a completely flexible polymer with self-avoidance, by Dubbledam et al. For a semi-flexible polymer with a persistence length P, its statistics is self-avoiding for a very long chain. As the local force increases, the blob size starts to decrease. At the blob size , where a is the size of a monomer, the statistics becomes that of an ideal chain. As the blob size further decreases to below the persistence length P, the statistics is that of a rigid rod. We argue that semi-flexible polymer in translocation should include the three regions: a self-avoiding region, an ideal chain region and a rigid rod region, under uneven tension propagation, instead of a uniform scaling picture as in the case of a completely flexible polymer. In various regimes under the effect of weak, intermediate and strong driving forces we derive equations from which we can calculate the translocation time of the polymer. The translocation exponent is given by , where is an effective exponent for the end-to-end distance of the semi-flexible polymer, having a value between 1/2 and 3/5, depending on the total contour length of the polymer. Our results are of relevance for forced translocation of biological polymers such as DNA through a nanopore.

Wrapping conformations of a polymer on a curved surface

NASA Astrophysics Data System (ADS)

Lin, Cheng-Hsiao; Tsai, Yan-Chr; Hu, Chin-Kun

2007-03-01

The conformation of a polymer on a curved surface is high on the agenda for polymer science. We assume that the free energy of the system is the sum of bending energy of the polymer and the electrostatic attraction between the polymer and surface. As is also assumed, the polymer is very stiff with an invariant length for each segment so that we can neglect its tensile energy and view its length as a constant. Based on the principle of minimization of free energy, we apply a variation method with a locally undetermined Lagrange multiplier to obtain a set of equations for the polymer conformation in terms of local geometrical quantities. We have obtained some numerical solutions for the conformations of the polymer chain on cylindrical and ellipsoidal surfaces. With some boundary conditions, we find that the free energy profiles of polymer chains behave differently and depend on the geometry of the surface for both cases. In the former case, the free energy of each segment distributes within a narrower range and its value per unit length oscillates almost periodically in the azimuthal angle. However, in the latter case the free energy distributes in a wider range with larger value at both ends and smaller value in the middle of the chain. The structure of a polymer wrapping around an ellipsoidal surface is apt to dewrap a polymer from the endpoints. The dependence of threshold lengths for a polymer on the initially anchored positions is also investigated. With initial conditions, the threshold wrapping length is found to increase with the electrostatic attraction strength for the ellipsoidal surface case. When a polymer wraps around a sphere surface, the threshold length increases monotonically with the radius without the self-intersection configuration for a polymer. We also discuss potential applications of the present theory to DNA/protein complex and further researches on DNA on the curved surface.

Polymer scaling and dynamics in steady-state sedimentation at infinite Péclet number.

PubMed

Lehtola, V; Punkkinen, O; Ala-Nissila, T

2007-11-01

We consider the static and dynamical behavior of a flexible polymer chain under steady-state sedimentation using analytic arguments and computer simulations. The model system comprises a single coarse-grained polymer chain of N segments, which resides in a Newtonian fluid as described by the Navier-Stokes equations. The chain is driven into nonequilibrium steady state by gravity acting on each segment. The equations of motion for the segments and the Navier-Stokes equations are solved simultaneously using an immersed boundary method, where thermal fluctuations are neglected. To characterize the chain conformation, we consider its radius of gyration RG(N). We find that the presence of gravity explicitly breaks the spatial symmetry leading to anisotropic scaling of the components of RG with N along the direction of gravity RG, parallel and perpendicular to it RG, perpendicular, respectively. We numerically estimate the corresponding anisotropic scaling exponents nu parallel approximately 0.79 and nu perpendicular approximately 0.45, which differ significantly from the equilibrium scaling exponent nue=0.588 in three dimensions. This indicates that on the average, the chain becomes elongated along the sedimentation direction for large enough N. We present a generalization of the Flory scaling argument, which is in good agreement with the numerical results. It also reveals an explicit dependence of the scaling exponents on the Reynolds number. To study the dynamics of the chain, we compute its effective diffusion coefficient D(N), which does not contain Brownian motion. For the range of values of N used here, we find that both the parallel and perpendicular components of D increase with the chain length N, in contrast to the case of thermal diffusion in equilibrium. This is caused by the fluid-driven fluctuations in the internal configuration of the polymer that are magnified as polymer size becomes larger.

A new paradigm for the molecular basis of rubber elasticity

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hanson, David E.; Barber, John L.

The molecular basis for rubber elasticity is arguably the oldest and one of the most important questions in the field of polymer physics. The theoretical investigation of rubber elasticity began in earnest almost a century ago with the development of analytic thermodynamic models, based on simple, highly-symmetric configurations of so-called Gaussian chains, i.e. polymer chains that obey Markov statistics. Numerous theories have been proposed over the past 90 years based on the ansatz that the elastic force for individual network chains arises from the entropy change associated with the distribution of end-to-end distances of a free polymer chain. There aremore » serious philosophical objections to this assumption and others, such as the assumption that all network nodes undergo affine motion and that all of the network chains have the same length. Recently, a new paradigm for elasticity in rubber networks has been proposed that is based on mechanisms that originate at the molecular level. Using conventional statistical mechanics analyses, quantum chemistry, and molecular dynamics simulations, the fundamental entropic and enthalpic chain extension forces for polyisoprene (natural rubber) have been determined, along with estimates for the basic force constants. Concurrently, the complex morphology of natural rubber networks (the joint probability density distributions that relate the chain end-to-end distance to its contour length) has also been captured in a numerical model. When molecular chain forces are merged with the network structure in this model, it is possible to study the mechanical response to tensile and compressive strains of a representative volume element of a polymer network. As strain is imposed on a network, pathways of connected taut chains, that completely span the network along strain axis, emerge. Although these chains represent only a few percent of the total, they account for nearly all of the elastic stress at high strain. Here we provide a brief review of previous elasticity theories and their deficiencies, and present a new paradigm with an emphasis on experimental comparisons.« less

A new paradigm for the molecular basis of rubber elasticity

DOE PAGES

Hanson, David E.; Barber, John L.

2015-02-19

The molecular basis for rubber elasticity is arguably the oldest and one of the most important questions in the field of polymer physics. The theoretical investigation of rubber elasticity began in earnest almost a century ago with the development of analytic thermodynamic models, based on simple, highly-symmetric configurations of so-called Gaussian chains, i.e. polymer chains that obey Markov statistics. Numerous theories have been proposed over the past 90 years based on the ansatz that the elastic force for individual network chains arises from the entropy change associated with the distribution of end-to-end distances of a free polymer chain. There aremore » serious philosophical objections to this assumption and others, such as the assumption that all network nodes undergo affine motion and that all of the network chains have the same length. Recently, a new paradigm for elasticity in rubber networks has been proposed that is based on mechanisms that originate at the molecular level. Using conventional statistical mechanics analyses, quantum chemistry, and molecular dynamics simulations, the fundamental entropic and enthalpic chain extension forces for polyisoprene (natural rubber) have been determined, along with estimates for the basic force constants. Concurrently, the complex morphology of natural rubber networks (the joint probability density distributions that relate the chain end-to-end distance to its contour length) has also been captured in a numerical model. When molecular chain forces are merged with the network structure in this model, it is possible to study the mechanical response to tensile and compressive strains of a representative volume element of a polymer network. As strain is imposed on a network, pathways of connected taut chains, that completely span the network along strain axis, emerge. Although these chains represent only a few percent of the total, they account for nearly all of the elastic stress at high strain. Here we provide a brief review of previous elasticity theories and their deficiencies, and present a new paradigm with an emphasis on experimental comparisons.« less

Conformational studies of the capsular polysaccharide produced by Neisseria meningitidis group A.

PubMed

Foschiatti, Michela; Hearshaw, Meredith; Cescutti, Paola; Ravenscroft, Neil; Rizzo, R

2009-05-12

The effect of different cations on the conformational and morphological properties of the capsular polysaccharide produced by Neisseria meningitidis group A was investigated. Circular dichroism studies showed that the presence of Na(+), NH4+ or Ca(2+) ions induced different local conformations of the polysaccharide chain through interactions with the phosphodiester group bridging the saccharide residues in the polymer chain. Atomic force microscopy experiments confirmed that the morphology of the polysaccharide chains was different depending on the nature of the counterion. Ammonium ions were associated with the presence of single polymer chains in an elongated conformation, whereas sodium ions favored the folding of the chains into a globular conformation. The addition of calcium ions produced the aggregation of a limited number of globular polysaccharide chains to form a 'toroidal-like' structure.

Tuning Adsorption Duration To Control the Diffusion of a Nanoparticle in Adsorbing Polymers.

PubMed

Cao, Xue-Zheng; Merlitz, Holger; Wu, Chen-Xu

2017-06-15

Controlling the nanoparticle (NP) diffusion in polymers is a prerequisite to obtain polymer nanocomposites (PNCs) with desired dynamical and rheological properties and to achieve targeted delivery of nanomedicine in biological systems. Here we determine the suppression mechanism of direct NP-polymer attraction to hamper the NP mobility in adsorbing polymers and then quantify the dependence of the effective viscosity η eff felt by the NP on the adsorption duration τ ads of polymers on the NP using scaling theory analysis and molecular dynamics simulations. We propose and confirm that participation of adsorbed chains in the NP motion break up at time intervals beyond τ ads due to the rearrangement of polymer segments at the NP surface, which accounts for the onset of Fickian NP diffusion on a time scale of t ≈ τ ads . We develop a power law, η eff ∼ (τ ads ) ν , where ν is the scaling exponent of the dependence of polymer coil size on the chain length, which leads to a theoretical basis for the design of PNCs and nanomedicine with desired applications through tuning the polymer adsorption duration.

Evolution of sequence-defined highly functionalized nucleic acid polymers

NASA Astrophysics Data System (ADS)

Chen, Zhen; Lichtor, Phillip A.; Berliner, Adrian P.; Chen, Jonathan C.; Liu, David R.

2018-03-01

The evolution of sequence-defined synthetic polymers made of building blocks beyond those compatible with polymerase enzymes or the ribosome has the potential to generate new classes of receptors, catalysts and materials. Here we describe a ligase-mediated DNA-templated polymerization and in vitro selection system to evolve highly functionalized nucleic acid polymers (HFNAPs) made from 32 building blocks that contain eight chemically diverse side chains on a DNA backbone. Through iterated cycles of polymer translation, selection and reverse translation, we discovered HFNAPs that bind proprotein convertase subtilisin/kexin type 9 (PCSK9) and interleukin-6, two protein targets implicated in human diseases. Mutation and reselection of an active PCSK9-binding polymer yielded evolved polymers with high affinity (KD = 3 nM). This evolved polymer potently inhibited the binding between PCSK9 and the low-density lipoprotein receptor. Structure-activity relationship studies revealed that specific side chains at defined positions in the polymers are required for binding to their respective targets. Our findings expand the chemical space of evolvable polymers to include densely functionalized nucleic acids with diverse, researcher-defined chemical repertoires.

Conductive polymer-based material

DOEpatents

McDonald, William F [Utica, OH; Koren, Amy B [Lansing, MI; Dourado, Sunil K [Ann Arbor, MI; Dulebohn, Joel I [Lansing, MI; Hanchar, Robert J [Charlotte, MI

2007-04-17

Disclosed are polymer-based coatings and materials comprising (i) a polymeric composition including a polymer having side chains along a backbone forming the polymer, at least two of the side chains being substituted with a heteroatom selected from oxygen, nitrogen, sulfur, and phosphorus and combinations thereof; and (ii) a plurality of metal species distributed within the polymer. At least a portion of the heteroatoms may form part of a chelation complex with some or all of the metal species. In many embodiments, the metal species are present in a sufficient concentration to provide a conductive material, e.g., as a conductive coating on a substrate. The conductive materials may be useful as the thin film conducting or semi-conducting layers in organic electronic devices such as organic electroluminescent devices and organic thin film transistors.

Specific Interaction between Redox Phospholipid Polymers and Plastoquinone in Photosynthetic Electron Transport Chain.

PubMed

Tanaka, Kenya; Kaneko, Masahiro; Ishikawa, Masahito; Kato, Souichiro; Ito, Hidehiro; Kamachi, Toshiaki; Kamiya, Kazuhide; Nakanishi, Shuji

2017-04-19

Redox phospholipid polymers added in culture media are known to be capable of extracting electrons from living photosynthetic cells across bacterial cell membranes with high cytocompatibility. In the present study, we identify the intracellular redox species that transfers electrons to the polymers. The open-circuit electrochemical potential of an electrolyte containing the redox polymer and extracted thylakoid membranes shift to positive (or negative) under light irradiation, when an electron transport inhibitor specific to plastoquinone is added upstream (or downstream) in the photosynthetic electron transport chain. The same trend is also observed for a medium containing living photosynthetic cells of Synechococcus elongatus PCC7942. These results clearly indicate that the phospholipid redox polymers extract photosynthetic electrons mainly from plastoquinone. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Turbulent drag reduction and degradation of DNA.

PubMed

Choi, H J; Lim, S T; Lai, Pik-Yin; Chan, C K

2002-08-19

Turbulent drag reduction induced by lambda-DNA is studied. The double-stranded DNA is found to be a good drag reducer when compared with the other normal linear polymers. However, this drag reducing power disappears when the DNA denatures to form two single-strand molecules. Mechanical degradation of DNA is also different from that of the normal linear-chain polymers: DNA is always cut in half by the turbulence. Our results suggest that the mechanism for turbulent degradation of DNA is different from that of the normal flexible long-chain polymers.

Ionochromic 4,4 '-azobispyridinium salt-incorporated polymer: synthesis and optical properties

NASA Astrophysics Data System (ADS)

Lee, Taek Seung; Ahn, Heungki; Lee, Jin Kyun; Park, Won Ho

2003-01-01

Azobispyridinium-bearing polyelectrolyte linked with flexible alkyl chain was synthesized and characterized. The polymer showed absorption changes upon addition of hydroxide anion with an isobestic point in UV-visible spectrum. It is presumed that conformational change of the azo group in the main chain is responsible for the point. Transduction of physical information (hydroxide concentration) into an optical signal from azo group was related to the ionochromic effect. Electrostatic self-assembled multilayer of the polymer with appropriate polyanion was carried out via layer-by-layer deposition.

Dynamics of polymer nanoparticles and chains.

NASA Astrophysics Data System (ADS)

Streletzky, Kiril; McKenna, John; Hillier, Gerry

2006-10-01

We present a Dynamic Light Scattering study of transport properties of the polymer chains and nanoparticles made out of the same starting solution. The spectra of both systems are highly non-exponential requiring a spectral time moment analysis. Our findings indicate the existence of several modes of relaxation in both systems. The comparison of the mean relaxation rates and diffusion coefficients of the different modes in two systems under good solvent conditions will be reported. Temperature sensitivity of the polymer nanoparticles and its possible applications in pharmaceutical, coatings, and petroleum industries will also be discussed.

What the ultimate polymeric electro-optic materials will be: guest-host, crosslinked, or side-chain?

NASA Astrophysics Data System (ADS)

Zhang, Cheng; Zhang, Hua; Oh, Min-Cheol; Dalton, Larry R.; Steier, William H.

2003-07-01

Material processing and device fabrication of many different electro-optic (EO) polymers developed at USC are reviewed. Detailed discussion is given to guest-host CLD/APCs, crosslinking perfluorocyclobutane (PFCB) polymer CX1, and thermally stable side-chain polymers CX2 and CX3. Excellent EO performance (1.4V at 1.31 μm, 2.1 V at 1.55 μm) was achieved in CLD/APC Mach-Zehnder modulators (2-cm, push-pull). CLD/APCs also possess low optical losses (1.2 dB/cm in slab waveguides and in thick core channel waveguides). However, the guest-host materials only have limited thermal stability (110-132 °C in short term, <60 °C in long term) and require special techniques in device fabrication. The crosslinking polymer CX1 was able to provide long-term stability at 85 oC when fully cured. It also has a low optical loss (comparable to CLD/APCs) before curing and decent EO coefficient when poled at 180 °C. However, after the films were poled at the crosslinking temperatures (200 °C or above), the transmissions of the waveguides and EO activity became very poor due to poling-induced chromophore degradation. By judicial molecular design of both chromophore and monomer structures to suppress thermal motion of polymer segments, we were able to realize the same or even better thermal stability in side-chain polymers CX2 and CX3. Since no curing is needed, devices can be poled at their optimal poling temperatures, and all good properties can be obtained simultaneously. Despite the excellent solubility in chlorinated solvents, these side-chain polymers are resistant to some other organic solvents or solutions such as acetone, photoresist and various UV-curable liquids.

Photophysics of conjugated polymers: interplay between Förster energy migration and defect concentration in shaping a photochemical funnel in PPV.

PubMed

Saini, Sangeeta; Bagchi, Biman

2010-07-21

Recent single molecule experiments have suggested the existence of a photochemical funnel in the photophysics of conjugated polymers, like poly[2-methoxy-5-(2'-ethylhexyl)oxy-1,4-phenylenevinylene] (MEH-PPV). The funnel is believed to be a consequence of the presence of conformational or chemical defects along the polymer chain and efficient non-radiative energy transfer among different chromophore segments. Here we address the effect of the excitation energy dynamics on the photophysics of PPV. The PPV chain is modeled as a polymer with the length distribution of chromophores given either by a Gaussian or by a Poisson distribution. We observe that the Poisson distribution of the segment lengths explains the photophysics of PPV better than the Gaussian distribution. A recently proposed version of an extended 'particle-in-a-box' model is used to calculate the exciton energies and the transition dipole moments of the chromophores, and a master equation to describe the excitation energy transfer among different chromophores. The rate of energy transfer is assumed to be given here, as a first approximation, by the well-known Förster expression. The observed excitation population dynamics confirms the photochemical funneling of excitation energy from shorter to longer chromophores of the polymer chain. The time scale of spectral shift and energy transfer for our model polymer, with realistic values of optical parameters, is in the range of 200-300 ps. We find that the excitation energy may not always migrate towards the longest chromophore segments in the polymer chain as the efficiency of energy transfer between chromophores depends on the separation distance between the two and their relative orientation.

Investigating the properties and interaction mechanism of nano-silica in polyvinyl alcohol/polyacrylamide blends at an atomic level.

PubMed

Wei, Qinghua; Wang, Yanen; Wang, Shuzhi; Zhang, Yingfeng; Chen, Xiongbiao

2017-11-01

The nano-silica can be incorporated into polymers for improved mechanical properties. Notably, the interaction between nano-silica and polymer is of a microscopic phenomenon and thus, hard to observe and study by using experimental methods. Based on molecular dynamics, this paper presents a study on the properties and the interaction mechanism of nano-silica in the polyvinyl alcohol (PVA)/polyacrylamide (PAM) blends at an atomic level. Specifically, six blends of PVA/PAM with varying concentrations of nano-silica (0-13wt%) and two interfacial interaction models of polymers on the silica surface were designed and analyzed at an atomic level in terms of concentration profile, mechanical properties, fractional free volume (FFV), dynamic properties of polymers and X-ray diffraction patterns. The concentration profile results and micromorphologies of equilibrium models suggest PAM molecular chains are easier to be adsorbed on the silica surface than PVA molecular chains in blends. The incorporation of nano-silica into the PVA/PAM blends can increase the blend mechanical properties, densities, and semicrystalline character. Meanwhile, the FFV and the mobility of polymer chain decrease with the silica concentration, which agrees with the results of mechanical properties, densities, and semicrystalline character. Our results also illustrate that an analysis of binding energies and pair correlation functions (PCF) allows for the discovery of the interaction mechanism of nano-silica in PVA/PAM blends; and that hydrogen bond interactions between polar functional groups of polymer molecular chains and the hydroxyl groups of the silica surface are involved in adsorption of the polymers on the silica surface, thus affecting the interaction mechanism of nano-silica in PVA/PAM blend systems. Copyright © 2017 Elsevier Ltd. All rights reserved.

Interfacial welding of dynamic covalent network polymers

NASA Astrophysics Data System (ADS)

Yu, Kai; Shi, Qian; Li, Hao; Jabour, John; Yang, Hua; Dunn, Martin L.; Wang, Tiejun; Qi, H. Jerry

2016-09-01

Dynamic covalent network (or covalent adaptable network) polymers can rearrange their macromolecular chain network by bond exchange reactions (BERs) where an active unit replaces a unit in an existing bond to form a new bond. Such macromolecular events, when they occur in large amounts, can attribute to unusual properties that are not seen in conventional covalent network polymers, such as shape reforming and surface welding; the latter further enables the important attributes of material malleability and powder-based reprocessing. In this paper, a multiscale modeling framework is developed to study the surface welding of thermally induced dynamic covalent network polymers. At the macromolecular network level, a lattice model is developed to describe the chain density evolution across the interface and its connection to bulk stress relaxation due to BERs. The chain density evolution rule is then fed into a continuum level interfacial model that takes into account surface roughness and applied pressure to predict the effective elastic modulus and interfacial fracture energy of welded polymers. The model yields particularly accessible results where the moduli and interfacial strength of the welded samples as a function of temperature and pressure can be predicted with four parameters, three of which can be measured directly. The model identifies the dependency of surface welding efficiency on the applied thermal and mechanical fields: the pressure will affect the real contact area under the consideration of surface roughness of dynamic covalent network polymers; the chain density increment on the real contact area of interface is only dependent on the welding time and temperature. The modeling approach shows good agreement with experiments and can be extended to other types of dynamic covalent network polymers using different stimuli for BERs, such as light and moisture etc.

Highly Stable, Anion Conductive, Comb-Shaped Copolymers for Alkaline Fuel Cells

DOE Office of Scientific and Technical Information (OSTI.GOV)

Li, NW; Leng, YJ; Hickner, MA

2013-07-10

To produce an anion-conductive and durable polymer electrolyte for alkaline fuel cell applications, a series of quaternized poly(2,6-dimethyl phenylene oxide)s containing long alkyl side chains pendant to the nitrogen-centered cation were synthesized using a Menshutkin reaction to form comb-shaped structures. The pendant alkyl chains were responsible for the development of highly conductive ionic domains, as confirmed by small-angle X-ray scattering (SAXS). The comb-shaped polymers having one alkyl side chain showed higher hydroxide conductivities than those with benzyltrimethyl ammonium moieties or structures with more than one alkyl side chain per cationic site. The highest conductivity was observed for comb-shaped polymers withmore » benzyldimethylhexadecyl ammonium cations. The chemical stabilities of the comb-shaped membranes were evaluated under severe, accelerated-aging conditions, and degradation was observed by measuring IEC and ion conductivity changes during aging. The comb-shaped membranes retained their high ion conductivity in 1 M NaOH at 80 degrees C for 2000 h. These cationic polymers were employed as ionomers in catalyst layers for alkaline fuel cells. The results indicated that the C-16 alkyl side chain ionomer had a slightly better initial performance, despite its low IEC value, but very poor durability in the fuel cell. In contrast, 90% of the initial performance was retained for the alkaline fuel cell with electrodes containing the C-6 side chain after 60 h of fuel cell operation.« less

Strong size-dependent stress relaxation in electrospun polymer nanofibers

NASA Astrophysics Data System (ADS)

Wingert, Matthew C.; Jiang, Zhang; Chen, Renkun; Cai, Shengqiang

2017-01-01

Electrospun polymer nanofibers have garnered significant interest due to their strong size-dependent material properties, such as tensile moduli, strength, toughness, and glass transition temperatures. These properties are closely correlated with polymer chain dynamics. In most applications, polymers usually exhibit viscoelastic behaviors such as stress relaxation and creep, which are also determined by the motion of polymer chains. However, the size-dependent viscoelasticity has not been studied previously in polymer nanofibers. Here, we report the first experimental evidence of significant size-dependent stress relaxation in electrospun Nylon-11 nanofibers as well as size-dependent viscosity of the confined amorphous regions. In conjunction with the dramatically increasing stiffness of nano-scaled fibers, this strong relaxation enables size-tunable properties which break the traditional damping-stiffness tradeoff, qualifying electrospun nanofibers as a promising set of size-tunable materials with an unusual and highly desirable combination of simultaneously high stiffness and large mechanical energy dissipation.

Highly ductile UV-shielding polymer composites with boron nitride nanospheres as fillers.

PubMed

Fu, Yuqiao; Huang, Yan; Meng, Wenjun; Wang, Zifeng; Bando, Yoshio; Golberg, Dmitri; Tang, Chengchun; Zhi, Chunyi

2015-03-20

Polymer composites with enhanced mechanical, thermal or optical performance usually suffer from poor ductility induced by confined mobility of polymer chains. Herein, highly ductile UV-shielding polymer composites are successfully fabricated. Boron nitride (BN) materials, with a wide band gap of around ∼6.0 eV, are used as fillers to achieve the remarkably improved UV-shielding performance of a polymer matrix. In addition, it is found that spherical morphology BN as a filler can keep the excellent ductility of the composites. For a comparison, it is demonstrated that traditional fillers, including conventional BN powders can achieve the similar UV-shielding performance but dramatically decrease the composite ductility. The mechanism behind this phenomenon is believed to be lubricant effects of BN nanospheres for sliding of polymer chains, which is in consistent with the thermal analyses. This study provides a new design to fabricate UV-shielding composite films with well-preserved ductility.

Self-Consistent Field Lattice Model for Polymer Networks.

PubMed

Tito, Nicholas B; Storm, Cornelis; Ellenbroek, Wouter G

2017-12-26

A lattice model based on polymer self-consistent field theory is developed to predict the equilibrium statistics of arbitrary polymer networks. For a given network topology, our approach uses moment propagators on a lattice to self-consistently construct the ensemble of polymer conformations and cross-link spatial probability distributions. Remarkably, the calculation can be performed "in the dark", without any prior knowledge on preferred chain conformations or cross-link positions. Numerical results from the model for a test network exhibit close agreement with molecular dynamics simulations, including when the network is strongly sheared. Our model captures nonaffine deformation, mean-field monomer interactions, cross-link fluctuations, and finite extensibility of chains, yielding predictions that differ markedly from classical rubber elasticity theory for polymer networks. By examining polymer networks with different degrees of interconnectivity, we gain insight into cross-link entropy, an important quantity in the macroscopic behavior of gels and self-healing materials as they are deformed.

Photocatalysts Based on Cobalt-Chelating Conjugated Polymers for Hydrogen Evolution from Water

DOE Office of Scientific and Technical Information (OSTI.GOV)

Li, Lianwei; Hadt, Ryan G.; Yao, Shiyu

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

Strong size-dependent stress relaxation in electrospun polymer nanofibers

DOE PAGES

Wingert, Matthew C.; Jiang, Zhang; Chen, Renkun; ...

2017-01-04

Here, electrospun polymer nanofibers have garnered significant interest due to their strong size-dependent material properties, such as tensile moduli, strength, toughness, and glass transition temperatures. These properties are closely correlated with polymer chain dynamics. In most applications, polymers usually exhibit viscoelastic behaviors such as stress relaxation and creep, which are also determined by the motion of polymer chains. However, the size-dependent viscoelasticity has not been studied previously in polymer nanofibers. Here, we report the first experimental evidence of significant size-dependent stress relaxation in electrospun Nylon-11 nanofibers as well as size-dependent viscosity of the confined amorphous regions. In conjunction with themore » dramatically increasing stiffness of nano-scaled fibers, this strong relaxation enables size-tunable properties which break the traditional damping-stiffness tradeoff, qualifying electrospun nanofibers as a promising set of size-tunable materials with an unusual and highly desirable combination of simultaneously high stiffness and large mechanical energy dissipation.« less

Solution rheology of polyelectrolytes and polyelectrolyte-surfactant systems

NASA Astrophysics Data System (ADS)

Plucktaveesak, Nopparat

The fundamental understanding of polyelectrolytes in aqueous solutions is an important branch of polymer research. In this work, the rheological properties of polyelectrolytes and polyelectrolyte/surfactant systems are studied. Various synthetic poly electrolytes are chosen with varied hydrophobicity. We discuss the effects of adding various surfactants to aqueous solutions of poly(ethylene oxide)-b-poly(propylene oxide)- b-polyethylene oxide)-g-poly(acrylic acid) (PEO-PPO-PAA) in the first chapter. Thermogelation in aqueous solutions of PEO-PPO-PAA is due to micellization caused by aggregation of poly(propylene oxide) (PPO) blocks resulting from temperature-induced dehydration of PPO. When nonionic surfactants with hydrophilic-lipophilic balance (HLB) parameter exceeding 11 or Cn alkylsulfates; n-octyl (C8), n-decyl (C 10) and n-dodecyl (C12) sulfates are added, the gelation threshold temperature (Tgel) of 1.0wt% PEO-PPO-PAA in aqueous solutions increases. In contrast, when nonionic surfactants with HLB below 11 are added, the gelation temperature decreases. On the other hand, alkylsulfates with n = 16 or 18 and poly(ethylene oxide) (PEO) do not affect the Tgel. The results imply that both hydrophobicity and tail length of the added surfactant play important roles in the interaction of PEO-PPO-PAA micelles and the surfactant. In the second chapter, the solution behavior of alternating copolymers of maleic acid and hydrophobic monomer is studied. The alternating structure of monomers with two-carboxylic groups and hydrophobic monomers make these copolymers unique. Under appropriate conditions, these carboxylic groups dissociate leaving charges on the chain. The potentiometric titrations of copolymer solutions with added CaCl2 reveal two distinct dissociation processes corresponding to the dissociation of the two adjacent carboxylic acids. The viscosity data as a function of polymer concentration of poly(isobutylene-alt-sodium maleate), poly(styrene-alt-sodium maleate) and poly(diisobutylene- alt-sodium maleate) show the polyelectrolyte behavior as predicted. However, the viscosity as a function of concentration of sodium maleate based copolymers with 1-alkenes; 1-octene (C8), 1-decene (C10), 1-dodecene (C12) and 1-hexene (C14) exhibit an abnormal scaling power, which might be caused by aggregation of the alkene tails to form micelles. In the last chapter, we report the rheological properties of aqueous solutions of poly(acrylic acid) and oppositely charged surfactant, dodecyl trimethylammonium bromide (C12TAB). The solution viscosity decreases as surfactant is added, partly because the polyelectrolyte wraps around the surface of the spherical surfactant micelles, shortening the effective chain length. The effects of polymer molecular weight, polymer concentration, and polymer charge have been studied with no added salt. The results are compared with the predictions of a simple model based on the scaling theory for the viscosity of dilute and unentangled semidilute polyelectrolyte solutions in good solvent. This model takes into account two effects of added surfactant. The effective chain length of the polyelectrolyte is shortened when a significant fraction of the chain wraps around micelles. Another effect is the change of solution ionic strength resulting from surfactant addition that further lowers the viscosity. The parameters used in this model are independently determined, allowing the model to make a quantitative prediction of solution viscosity with no adjustable parameters. The model is also applied to predict the decrease in viscosity of various polyelectrolyte/oppositely charged surfactant systems reported in literature. The results are in good agreement with experimental data, proving that our model applies to all polyelectrolytes mixed with oppositely charged surfactants that form spherical micelles.

Generalized theory of semiflexible polymers.

PubMed

Wiggins, Paul A; Nelson, Philip C

2006-03-01

DNA bending on length scales shorter than a persistence length plays an integral role in the translation of genetic information from DNA to cellular function. Quantitative experimental studies of these biological systems have led to a renewed interest in the polymer mechanics relevant for describing the conformational free energy of DNA bending induced by protein-DNA complexes. Recent experimental results from DNA cyclization studies have cast doubt on the applicability of the canonical semiflexible polymer theory, the wormlike chain (WLC) model, to DNA bending on biologically relevant length scales. This paper develops a theory of the chain statistics of a class of generalized semiflexible polymer models. Our focus is on the theoretical development of these models and the calculation of experimental observables. To illustrate our methods, we focus on a specific, illustrative model of DNA bending. We show that the WLC model generically describes the long-length-scale chain statistics of semiflexible polymers, as predicted by renormalization group arguments. In particular, we show that either the WLC or our present model adequately describes force-extension, solution scattering, and long-contour-length cyclization experiments, regardless of the details of DNA bend elasticity. In contrast, experiments sensitive to short-length-scale chain behavior can in principle reveal dramatic departures from the linear elastic behavior assumed in the WLC model. We demonstrate this explicitly by showing that our toy model can reproduce the anomalously large short-contour-length cyclization factors recently measured by Cloutier and Widom. Finally, we discuss the applicability of these models to DNA chain statistics in the context of future experiments.

A non-affine micro-macro approach to strain-crystallizing rubber-like materials

NASA Astrophysics Data System (ADS)

Rastak, Reza; Linder, Christian

2018-02-01

Crystallization can occur in rubber materials at large strains due to a phenomenon called strain-induced crystallization. We propose a multi-scale polymer network model to capture this process in rubber-like materials. At the microscopic scale, we present a chain formulation by studying the thermodynamic behavior of a polymer chain and its crystallization mechanism inside a stretching polymer network. The chain model accounts for the thermodynamics of crystallization and presents a rate-dependent evolution law for crystallization based on the gradient of the free energy with respect to the crystallinity variables to ensures the dissipation is always non-negative. The multiscale framework allows the anisotropic crystallization of rubber which has been observed experimentally. Two different approaches for formulating the orientational distribution of crystallinity are studied. In the first approach, the algorithm tracks the crystallization at a finite number of orientations. In contrast, the continuous distribution describes the crystallization for all polymer chain orientations and describes its evolution with only a few distribution parameters. To connect the deformation of the micro with that of the macro scale, our model combines the recently developed maximal advance path constraint with the principal of minimum average free energy, resulting in a non-affine deformation model for polymer chains. Various aspects of the proposed model are validated by existing experimental results, including the stress response, crystallinity evolution during loading and unloading, crystallinity distribution, and the rotation of the principal crystallization direction. As a case study, we simulate the formation of crystalline regions around a pre-existing notch in a 3D rubber block and we compare the results with experimental data.

Modular in situ-Functionalization Strategy: Multicomponent Polymerization via Palladium/Norbornene Cooperative Catalysis.

PubMed

Yoon, Ki-Young; Dong, Guangbin

2018-05-23

Herein, we report the palladium/norbornene cooperatively catalyzed polymerization, which simplifies synthesis of functional aromatic polymers, including conjugated polymers. Specifically, an A2B2C-type multicomponent polymerization is developed using ortho-amination/ipso-alkynylation reaction for preparing various amine-functionalized arylacetylene-containing polymers. Within a single catalytic cycle, the amine side-chains are site-selectively installed in situ via C-H activation during the polymerization process, which represents a major difference from conventional cross-coupling polymerizations. This in situ-functionalization strategy enables modular incorporation of functional side-chains from simple monomers, thereby conveniently affording a diverse range of functional polymers. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Searching for low percolation thresholds within amphiphilic polymer membranes: The effect of side chain branching

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dorenbos, G., E-mail: dorenbos@ny.thn.ne.jp

Percolation thresholds for solvent diffusion within hydrated model polymeric membranes are derived from dissipative particle dynamics in combination with Monte Carlo (MC) tracer diffusion calculations. The polymer backbones are composed of hydrophobic A beads to which at regular intervals Y-shaped side chains are attached. Each side chain is composed of eight A beads and contains two identical branches that are each terminated with a pendant hydrophilic C bead. Four types of side chains are considered for which the two branches (each represented as [C], [AC], [AAC], or [AAAC]) are splitting off from the 8th, 6th, 4th, or 2nd A bead,more » respectively. Water diffusion through the phase separated water containing pore networks is deduced from MC tracer diffusion calculations. The percolation threshold for the architectures containing the [C] and [AC] branches is at a water volume fraction of ∼0.07 and 0.08, respectively. These are much lower than those derived earlier for linear architectures of various side chain length and side chain distributions. Control of side chain architecture is thus a very interesting design parameter to decrease the percolation threshold for solvent and proton transports within flexible amphiphilic polymer membranes.« less

PEG-poly(amino acid) block copolymer micelles for tunable drug release.

PubMed

Ponta, Andrei; Bae, Younsoo

2010-11-01

To achieve tunable pH-dependent drug release in tumor tissues. Poly(ethylene glycol)-poly(aspartic acid) [PEG-p(Asp)] containing 12 kDa PEG and pAsp (5, 15, and 35 repeating units) were prepared. Hydrazide linkers with spacers [glycine (Gly) and 4-aminobenzoate (Abz)] were introduced to PEG-p(Asp), followed by drug conjugation [doxorubicin (DOX)]. The block copolymer-drug conjugates were either reconstituted or dialyzed in aqueous solutions to prepare micelles. Drug release patterns were observed under sink conditions at pH 5.0 and 7.4, 37°C, for 48 h. A collection of six block copolymers with different chain lengths and spacers was synthesized. Drug binding yields were 13-43.6%. The polymer-drug conjugates formed <50 nm polymer micelles irrespective of polymer compositions. Gly-introduced polymer micelles showed marginal change in particle size (40 ± 10 nm), while the size of Abz-micelles increased gradually from 10 to 40 nm as the polymer chain lengths increased. Drug release patterns of both Gly and Abz micelles were pH-dependent and tunable. The spacers appear to play a crucial role in controlling drug release and stability of polymer micelles in combination with block copolymer chain lengths. A drug delivery platform for tunable drug release was successfully developed with polymer micelles possessing spacer-modified hydrazone drug-binding linkers.

Conformational features of cepacian: the exopolysaccharide produced by clinical strains of Burkholderia cepacia.

PubMed

Nogueira, Carlos E Sampaio; Ruggiero, Jose R; Sist, Paola; Cescutti, Paola; Urbani, Ranieri; Rizzo, Roberto

2005-04-11

Conformational energy calculations and molecular dynamics investigations, both in water and in dimethyl sulfoxide, were carried out on the exopolysaccharide cepacian produced by the majority of the clinical strains of Burkholderia cepacia, an opportunistic pathogen causing serious lung infection in patients affected by cystic fibrosis, The investigation was aimed at defining the structural and conformational features, which might be relevant for clarification of the structure-function relationships of the polymer. The molecular dynamics calculations were carried out by Ramachandran-type energy plots of the disaccharides that constitute the polymer repeating unit. The dynamics of an oligomer composed of three repeating units were investigated in water and in Me2SO, a non-aggregating solvent. Analysis of the time persistence of hydrogen bonds showed the presence of a large number of favourable interactions in water, which were less evident in Me2SO. The calculations on the cepacian chain indicated that polymer conformational features in water were affected by the lateral chains, but were also largely dictated by the presence of solvent. Moreover, the large number of intra-chain hydrogen bonds in water disappeared in Me2SO solution, increasing the average dimension of the polymer chains.

Disentangling the Role of Entanglement Density and Molecular Alignment in the Mechanical Response of Glassy Polymers

NASA Astrophysics Data System (ADS)

O'Connor, Thomas; Robbins, Mark

Glassy polymers are a ubiquitous part of modern life, but much about their mechanical properties remains poorly understood. Since chains in glassy states are hindered from exploring their conformational entropy, they can't be understood with common entropic network models. Additionally, glassy states are highly sensitive to material history and nonequilibrium distributions of chain alignment and entanglement can be produced during material processing. Understanding how these far-from equilibrium states impact mechanical properties is analytically challenging but essential to optimizing processing methods. We use molecular dynamics simulations to study the yield and strain hardening of glassy polymers as separate functions of the degree of molecular alignment and inter-chain entanglement. We vary chain alignment and entanglement with three different preparation protocols that mimic common processing conditions in and out of solution. We compare our results to common mechanical models of amorphous polymers and assess their applicability to different experimental processing conditions. This research was performed within the Center for Materials in Extreme Dynamic Environments (CMEDE) under the Hopkins Extreme Materials Institute at Johns Hopkins University. Financial support was provided by Grant W911NF-12-2-0022.

Effect of Chain Rigidity on the Decoupling of Ion Motion from Segmental Relaxation in Polymerized Ionic Liquids: Ambient and Elevated Pressure Studies

DOE PAGES

Wojnarowska, Zaneta; Feng, Hongbo; Fu, Yao; ...

2017-08-21

Conductivity in polymer electrolytes has been generally discussed with the assumption that the segmental motions control charge transport. However, much less attention has been paid to the mechanism of ion conductivity where the motions of ions are less dependent (decoupled) on segmental dynamics. We present that this phenomenon is observed in ionic materials as they approach their glass transition temperature and becomes essential for design and development of highly conducting solid polymer electrolytes. In this paper, we study the effect of chain rigidity on the decoupling of ion transport from segmental motion in three polymerized ionic liquids (polyILs) containing themore » same cation–anion pair but differing in flexibility of the polymer backbones and side groups. Analysis of dielectric and rheology data reveals that decoupling is strong in vinyl-based rigid polymers while almost negligible in novel siloxane-based flexible polyILs. To explain this behavior, we investigated ion and chain dynamics at ambient and elevated pressure. Our results suggest that decoupling has a direct relationship to the frustration in chain packing and free volume. Finally, these conclusions are also supported by coarse-grained molecular dynamics simulations.« less

A molecular model for cohesive slip at polymer melt/solid interfaces.

PubMed

Tchesnokov, M A; Molenaar, J; Slot, J J M; Stepanyan, R

2005-06-01

A molecular model is proposed which predicts wall slip by disentanglement of polymer chains adsorbed on a wall from those in the polymer bulk. The dynamics of the near-wall boundary layer is found to be governed by a nonlinear equation of motion, which accounts for such mechanisms on surface chains as convection, retraction, constraint release, and thermal fluctuations. This equation is valid over a wide range of grafting regimes, including those in which interactions between neighboring adsorbed molecules become essential. It is not closed since the dynamics of adsorbed chains is shown to be coupled to that of polymer chains in the bulk via constraint release. The constitutive equations for the layer and bulk, together with continuity of stress and velocity, are found to form a closed system of equations which governs the dynamics of the whole "bulk+boundary layer" ensemble. Its solution provides a stick-slip law in terms of the molecular parameters and extruder geometry. The model is quantitative and contains only those parameters that can be measured directly, or extracted from independent rheological measurements. The model predictions show a good agreement with available experimental data.

Effect of Chain Rigidity on the Decoupling of Ion Motion from Segmental Relaxation in Polymerized Ionic Liquids: Ambient and Elevated Pressure Studies

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wojnarowska, Zaneta; Feng, Hongbo; Fu, Yao

Conductivity in polymer electrolytes has been generally discussed with the assumption that the segmental motions control charge transport. However, much less attention has been paid to the mechanism of ion conductivity where the motions of ions are less dependent (decoupled) on segmental dynamics. We present that this phenomenon is observed in ionic materials as they approach their glass transition temperature and becomes essential for design and development of highly conducting solid polymer electrolytes. In this paper, we study the effect of chain rigidity on the decoupling of ion transport from segmental motion in three polymerized ionic liquids (polyILs) containing themore » same cation–anion pair but differing in flexibility of the polymer backbones and side groups. Analysis of dielectric and rheology data reveals that decoupling is strong in vinyl-based rigid polymers while almost negligible in novel siloxane-based flexible polyILs. To explain this behavior, we investigated ion and chain dynamics at ambient and elevated pressure. Our results suggest that decoupling has a direct relationship to the frustration in chain packing and free volume. Finally, these conclusions are also supported by coarse-grained molecular dynamics simulations.« less

Resin blending for toughness in balloon films

NASA Technical Reports Server (NTRS)

Farr, M. P.; Harrison, I. R.

1993-01-01

The influence of chain architecture on toughness is examined by testing blends of HDPE with different types of low density PEs. The LDPE and LLDPE used have reported similar molecular weights, and densities. Two structural factors differentiate these polymers, long chain branching is peculiar to LDPE, and the short chain branching distribution of the two polymers are different. LDPE has branches which are evenly distributed among all chains. In contrast, the short chain branches in LLDPE are distributed heterogeneously. LLDPE and ULDPE have similar branch distributions but, ULDPE has a higher average number of branches per 1000 carbons and consequently a lower density. The effect which these structural differences have on mechanical properties can be used to investigate which parameters control toughness in PE materials.

Solution-processable ambipolar diketopyrrolopyrrole-selenophene polymer with unprecedentedly high hole and electron mobilities.

PubMed

Lee, Junghoon; Han, A-Reum; Kim, Jonggi; Kim, Yiho; Oh, Joon Hak; Yang, Changduk

2012-12-26

There is a fast-growing demand for polymer-based ambipolar thin-film transistors (TFTs), in which both n-type and p-type transistor operations are realized in a single layer, while maintaining simplicity in processing. Research progress toward this end is essentially fueled by molecular engineering of the conjugated backbones of the polymers and the development of process architectures for device fabrication, which has recently led to hole and electron mobilities of more than 1.0 cm(2) V(-1) s(-1). However, ambipolar polymers with even higher performance are still required. By taking into account both the conjugated backbone and side chains of the polymer component, we have developed a dithienyl-diketopyrrolopyrrole (TDPP) and selenophene containing polymer with hybrid siloxane-solubilizing groups (PTDPPSe-Si). A synergistic combination of rational polymer backbone design, side-chain dynamics, and solution processing affords an enormous boost in ambipolar TFT performance, resulting in unprecedentedly high hole and electron mobilities of 3.97 and 2.20 cm(2) V(-1) s(-1), respectively.

The local phase transitions of the solvent in the neighborhood of a solvophobic polymer at high pressures

DOE Office of Scientific and Technical Information (OSTI.GOV)

Budkov, Yu. A., E-mail: urabudkov@rambler.ru; National Research University Higher School of Economics, Moscow; Department of Chemistry, Lomonosov Moscow State University, Moscow

2014-11-28

We investigate local phase transitions of the solvent in the neighborhood of a solvophobic polymer chain which is induced by a change of the polymer-solvent repulsion and the solvent pressure in the bulk solution. We describe the polymer in solution by the Edwards model, where the conditional partition function of the polymer chain at a fixed radius of gyration is described by a mean-field theory. The contributions of the polymer-solvent and the solvent-solvent interactions to the total free energy are described within the mean-field approximation. We obtain the total free energy of the solution as a function of the radiusmore » of gyration and the average solvent number density within the gyration volume. The resulting system of coupled equations is solved varying the polymer-solvent repulsion strength at high solvent pressure in the bulk. We show that the coil-globule (globule-coil) transition occurs accompanied by a local solvent evaporation (condensation) within the gyration volume.« less

Electrical degradation of triarylamine-based light-emitting polymer diodes monitored by micro-Raman spectroscopy

NASA Astrophysics Data System (ADS)

Kim, Ji-Seon; Ho, Peter K. H.; Murphy, Craig E.; Seeley, Alex J. A. B.; Grizzi, Ilaria; Burroughes, Jeremy H.; Friend, Richard H.

2004-03-01

Although much progress has been made in improving polymer light-emitting diode performance, there has been little work to address device intrinsic degradation mechanisms due to the challenge of tracking minute chemical reactions in the 100-nm-thick buried active layers during operation. Here we have elucidated a hole-mediated electrical degradation of triarylamine-based blue polymer diodes using in situ Raman microspectroscopy. A slow irreversible hole-doping of polymer adjacent to the hole-injecting conducting-polymer leads to formation of oxidised triarylamine species counterbalanced by anions from the conducting-polymer. These charged species act as luminescence quenchers and hinder further hole injection across the interface leading to significant decreases in current density at low voltages.

Foldamer hypothesis for the growth and sequence differentiation of prebiotic polymers

DOE Office of Scientific and Technical Information (OSTI.GOV)

Guseva, Elizaveta; Zuckermann, Ronald N.; Dill, Ken A.

It is not known how life originated. It is thought that prebiotic processes were able to synthesize short random polymers. However, then, how do short-chain molecules spontaneously grow longer? Also, how would random chains grow more informational and become autocatalytic (i.e., increasing their own concentrations)? We study the folding and binding of random sequences of hydrophobic ( H) and polar ( P) monomers in a computational model. We find that even short hydrophobic polar ( HP) chains can collapse into relatively compact structures, exposing hydrophobic surfaces. In this way, they act as primitive versions of today’s protein catalysts, elongating othermore » such HP polymers as ribosomes would now do. Such foldamer catalysts are shown to form an autocatalytic set, through which short chains grow into longer chains that have particular sequences. An attractive feature of this model is that it does not overconverge to a single solution; it gives ensembles that could further evolve under selection. This mechanism describes how specific sequences and conformations could contribute to the chemistry-to-biology (CTB) transition.« less

Foldamer hypothesis for the growth and sequence differentiation of prebiotic polymers

DOE PAGES

Guseva, Elizaveta; Zuckermann, Ronald N.; Dill, Ken A.

2017-08-22

It is not known how life originated. It is thought that prebiotic processes were able to synthesize short random polymers. However, then, how do short-chain molecules spontaneously grow longer? Also, how would random chains grow more informational and become autocatalytic (i.e., increasing their own concentrations)? We study the folding and binding of random sequences of hydrophobic ( H) and polar ( P) monomers in a computational model. We find that even short hydrophobic polar ( HP) chains can collapse into relatively compact structures, exposing hydrophobic surfaces. In this way, they act as primitive versions of today’s protein catalysts, elongating othermore » such HP polymers as ribosomes would now do. Such foldamer catalysts are shown to form an autocatalytic set, through which short chains grow into longer chains that have particular sequences. An attractive feature of this model is that it does not overconverge to a single solution; it gives ensembles that could further evolve under selection. This mechanism describes how specific sequences and conformations could contribute to the chemistry-to-biology (CTB) transition.« less

Foldamer hypothesis for the growth and sequence differentiation of prebiotic polymers

PubMed Central

Guseva, Elizaveta; Zuckermann, Ronald N.; Dill, Ken A.

2017-01-01

It is not known how life originated. It is thought that prebiotic processes were able to synthesize short random polymers. However, then, how do short-chain molecules spontaneously grow longer? Also, how would random chains grow more informational and become autocatalytic (i.e., increasing their own concentrations)? We study the folding and binding of random sequences of hydrophobic (H) and polar (P) monomers in a computational model. We find that even short hydrophobic polar (HP) chains can collapse into relatively compact structures, exposing hydrophobic surfaces. In this way, they act as primitive versions of today’s protein catalysts, elongating other such HP polymers as ribosomes would now do. Such foldamer catalysts are shown to form an autocatalytic set, through which short chains grow into longer chains that have particular sequences. An attractive feature of this model is that it does not overconverge to a single solution; it gives ensembles that could further evolve under selection. This mechanism describes how specific sequences and conformations could contribute to the chemistry-to-biology (CTB) transition. PMID:28831002

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.

Simultaneous Enhancements of Conductivity and Stability for Anion Exchange Membranes (AEMs) through Precise Structure Design

PubMed Central

Ran, Jin; Wu, Liang; Wei, Bing; Chen, Yaoyao; Xu, Tongwen

2014-01-01

Polymeric materials as anion exchange membranes (AEMs) play an essential role in the field of energy and environment. The achievement of high performance AEMs by the precise manipulation of macromolecular architecture remains a daunting challenge. Herein, we firstly report a novel rod-coil graft copolymer AEM, possessing rigid hydrophobic main chains and soft hydrophilic graft chains. The low graft density, which can alleviate the adverse influences of ioinc graft chains on the main chains, was obtained by using the living polymerization technique. Consequently, the grafted ionic groups which result in the degradation of polymer backbone was decreased to a small degree. Moreover, the relatively long graft chains induced the nanophase separation between the hydrophobic polymer chains and hydrophilic graft chains, which creates a convinient pathway for high hydroxide ion mobility. Such an accurate molecular design simultaneously improves the hydroxide ion conductivity and alkaline stability as well as dimensional stability. PMID:25255843

Simultaneous Enhancements of Conductivity and Stability for Anion Exchange Membranes (AEMs) through Precise Structure Design

NASA Astrophysics Data System (ADS)

Ran, Jin; Wu, Liang; Wei, Bing; Chen, Yaoyao; Xu, Tongwen

2014-09-01

Polymeric materials as anion exchange membranes (AEMs) play an essential role in the field of energy and environment. The achievement of high performance AEMs by the precise manipulation of macromolecular architecture remains a daunting challenge. Herein, we firstly report a novel rod-coil graft copolymer AEM, possessing rigid hydrophobic main chains and soft hydrophilic graft chains. The low graft density, which can alleviate the adverse influences of ioinc graft chains on the main chains, was obtained by using the living polymerization technique. Consequently, the grafted ionic groups which result in the degradation of polymer backbone was decreased to a small degree. Moreover, the relatively long graft chains induced the nanophase separation between the hydrophobic polymer chains and hydrophilic graft chains, which creates a convinient pathway for high hydroxide ion mobility. Such an accurate molecular design simultaneously improves the hydroxide ion conductivity and alkaline stability as well as dimensional stability.

Influence of macromolecular architecture on necking in polymer extrusion film casting process

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pol, Harshawardhan; Banik, Sourya; Azad, Lal Busher

2015-05-22

Extrusion film casting (EFC) is an important polymer processing technique that is used to produce several thousand tons of polymer films/coatings on an industrial scale. In this research, we are interested in understanding quantitatively how macromolecular chain architecture (for example long chain branching (LCB) or molecular weight distribution (MWD or PDI)) influences the necking and thickness distribution of extrusion cast films. We have used different polymer resins of linear and branched molecular architecture to produce extrusion cast films under controlled experimental conditions. The necking profiles of the films were imaged and the velocity profiles during EFC were monitored using particlemore » tracking velocimetry (PTV) technique. Additionally, the temperature profiles were captured using an IR thermography and thickness profiles were calculated. The experimental results are compared with predictions of one-dimensional flow model of Silagy et al{sup 1} wherein the polymer resin rheology is modeled using molecular constitutive equations such as the Rolie-Poly (RP) and extended Pom Pom (XPP). We demonstrate that the 1-D flow model containing the molecular constitutive equations provides new insights into the role of macromolecular chain architecture on film necking.{sup 1}D. Silagy, Y. Demay, and J-F. Agassant, Polym. Eng. Sci., 36, 2614 (1996)« less

Adsorption and flocculation by polymers and polymer mixtures.

PubMed

Gregory, John; Barany, Sandor

2011-11-14

Polymers of various types are in widespread use as flocculants in several industries. In most cases, polymer adsorption is an essential prerequisite for flocculation and kinetic aspects are very important. The rates of polymer adsorption and of re-conformation (relaxation) of adsorbed chains are key factors that influence the performance of flocculants and their mode of action. Polyelectrolytes often tend to adopt a rather flat adsorbed configuration and in this state their action is mainly through charge effects, including 'electrostatic patch' attraction. When the relaxation rate is quite low, particle collisions may occur while the adsorbed chains are still in an extended state and flocculation by polymer bridging may occur. These effects are now well understood and supported by much experimental evidence. In recent years there has been considerable interest in the use of multi-component flocculants, especially dual-polymer systems. In the latter case, there can be significant advantages over the use of single polymers. Despite some complications, there is a broad understanding of the action of dual polymer systems. In many cases the sequence of addition of the polymers is important and the pre-adsorbed polymer can have two important effects: providing adsorption sites for the second polymer or causing a more extended adsorbed conformation as a result of 'site blocking'. Copyright © 2011 Elsevier B.V. All rights reserved.

Dynamic covalent polymers

PubMed Central

García, Fátima

2016-01-01

ABSTRACT This Highlight presents an overview of the rapidly growing field of dynamic covalent polymers. This class of polymers combines intrinsic reversibility with the robustness of covalent bonds, thus enabling formation of mechanically stable, polymer‐based materials that are responsive to external stimuli. It will be discussed how the inherent dynamic nature of the dynamic covalent bonds on the molecular level can be translated to the macroscopic level of the polymer, giving access to a range of applications, such as stimuli‐responsive or self‐healing materials. A primary distinction will be made based on the type of dynamic covalent bond employed, while a secondary distinction will be based on the consideration whether the dynamic covalent bond is used in the main chain of the polymer or whether it is used to allow side chain modification of the polymer. Emphasis will be on the chemistry of the dynamic covalent bonds present in the polymer, in particular in relation to how the specific (dynamic) features of the bond impart functionality to the polymer material, and to the conditions under which this dynamic behavior is manifested. © 2016 The Authors. Journal of Polymer Science Part A: Polymer Chemistry Published by Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016, 54, 3551–3577. PMID:27917019

Amphiphilic graft polymer with reduction breakable main chain prepared via click polymerization and grafting onto

NASA Astrophysics Data System (ADS)

Zhang, Xiaojin; Dai, Yu

2018-06-01

Amphiphilic graft polymer PSS- g-Pal/PEG with reduction breakable main chain was synthesized via click polymerization of dialkynyl (containing disulfide bond) and diazide (containing pendant diol) and one-pot grafting onto of hydrophobic palmitate (Pal) and hydrophilic methoxy poly(ethylene glycol) (PEG). PSS- g-Pal/PEG is able to form polymeric micelles by self-assembly in water via dialysis. Polymeric micelles are nano-sized spheres and the particle size is approximately 70 nm. Of note, polymeric micelles are reduction-responsive owing to the disulfide bonds in main chain of PSS- g-Pal/PEG. Therefore, polymeric micelles prepared from amphiphilic graft polymer PSS- g-Pal/PEG are able to fast release the drugs in the presence of the reducing agents such as DL-dithiothreitol (DTT).

Self-interacting polymer chains terminally anchored to adsorbing surfaces of three-dimensional fractal lattices

NASA Astrophysics Data System (ADS)

Živić, I.; Elezović-Hadžić, S.; Milošević, S.

2018-01-01

We have studied the adsorption problem of self-attracting linear polymers, modeled by self-avoiding walks (SAWs), situated on three-dimensional fractal structures, exemplified by 3d Sierpinski gasket (SG) family of fractals as containers of a poor solvent. Members of SG family are enumerated by an integer b (b ≥ 2), and it is assumed that one side of each SG fractal is an impenetrable adsorbing surface. We calculate the critical exponents γ1 ,γ11, and γs, which are related to the numbers of all possible SAWs with one, both, and no ends anchored to the adsorbing boundary, respectively. By applying the exact renormalization group (RG) method (for the first three members of the SG fractal family, b = 2 , 3, and 4), we have obtained specific values of these exponents, for θ-chain and globular polymer phase. We discuss their mutual relations and relations with corresponding values pertinent to extended polymer chain phase.

How does low-molecular-weight polystyrene dissolve: osmotic swelling vs. surface dissolution.

PubMed

Marcon, Valentina; van der Vegt, Nico F A

2014-12-07

By means of multiscale hierarchical modeling we study the real time evolution of low-molecular-weight polystyrene, below the glass transition temperature, in contact with its solvent, toluene. We observe two concurrent phenomena taking place: (1) the solvent diffuses into the polymer by a Case II mechanism, leading to osmotic driven swelling and progressive chain dilution (inside-out mechanism); (2) polymer chains are solvated, detach from the interface and move into the solvent before the film is completely swollen (outside-in mechanism). From our simulations we conclude that, below the entanglement length, a thin swollen layer, also observed in previous experiments, forms almost instantaneously, which allows for the outside-in mechanism to start a few tens of nanoseconds after the polymer-solvent initial contact. After this initial transient time the two mechanisms are concurrent. We furthermore observe that the presence of the solvent significantly enhances the mobility of the polymer chains of the surface layer, but only in the direction parallel to the interface.

Associative polymers bridging between layers of multilamellar vesicles.

NASA Astrophysics Data System (ADS)

Choi, Seo; Bhatia, Surita

2006-03-01

Multilamellar vesicles can be found in a variety of pharmaceutical formulations, personal care products, and home care products. Hydrophobically modified associative polymers are often used to stabilize the vesicles or to control the rheological properties of these formulations. The hydrophobic groups are expected to insert themselves into the vesicle bilayers. Recent experimental work shows that hydrophobically modified polymers may from bridges between vesicles or may bridge between layers of a single vesicle. The latter configuration forces an interlayer spacing roughly equal to the radius of gyration of the backbone between associative groups. We have performed simple mean-field calculations on ideal telechelic associative polymers between concentric spherical surfaces. We find that the free energy per chain has an attractive minimum when the layer spacing is approximately N^1/2l, which is consistent with experimental results. The depth of the minimum depends on both chain length and curvature, and as expected when the curvature becomes small, the result for telechelic chains between flat surfaces is recovered.

Correlating morphology to dc conductivity in polymerized ionic liquids

NASA Astrophysics Data System (ADS)

Iacob, Ciprian; Matusmoto, Atsushi; Inoue, Tadashi; Runt, James

Polymerized ionic liquids (PILs) combine the attractive mechanical characteristics of polymers and unique physico-chemical properties of low molecular weight ionic liquids in the same material. PILs have shown remarkable advantages when employed in electrochemical devices such as dye-sensitized solar cells and lithium batteries, among others. Understanding their ionic transport mechanism is the key for designing highly conductive PILs. In the current study, the correlation between morphology and charge transport in two homologous series of PILs with systematic variation of the alkyl chain length and anions is investigated using broadband dielectric spectroscopy, rheology, differential scanning calorimetry and X-ray scattering. As the alkyl chain length increases, the backbone-to-backbone separation increases, and dc-conductivity consequently decreases. The cations dominate structural dynamics since they are attached to the polymer chains, while the anions are smaller and more mobile ionic species thereby controlling the ionic conductivity. Further interpretation of decoupling of dc conductivity from the segmental relaxation enabled the correlation between polymer morphology and dc conductivity. Supported by the National Science Foundation, Polymers Program.

Local Dynamics of Acid- and Ion-containing Copolymer Melts

NASA Astrophysics Data System (ADS)

Winey, Karen; Middleton, Robert; Tarver, Jacob; Tyagi, Madhusudan; Soles, Christopher; Frischknecht, Amalie

Interest in acid- and ion-containing polymers arises in part from applications as single-ion conductors for selectively transporting a counter ion for battery applications. Structurally, the low dielectric constant of organic polymers and strong ionic interactions leads to ionic aggregation. Here the polymer backbone motion was investigated through quasi-elastic neutron scattering measurements (QENS) and compared with fully atomistic molecular dynamic simulations of precise poly(ethylene-acrylic acid) copolymers and their ionomers (pxAA-y%Li). The effect of carbon spacer length (x =9, 15, 21) between the acid groups and the degree of neutralization (y) with Li on PE backbone dynamics were considered. Systematic slowing in chain dynamics were observed with increasing neutralization where polymer dynamics appear constrained due to anchoring effects. Simulations provide complementary viewpoints indicating a gradient in chain dynamics as a distance away from acid groups. These results indicate that the addition of pendant acid groups inhibit typical PE backbone motion and the neutralized forms strongly suppress the fraction of mobile PE chain.

The effect of chain rigidity on the interfacial layer thickness and dynamics of polymer nanocomposites

NASA Astrophysics Data System (ADS)

Cheng, Shiwang; Carrillo, Jan-Michael Y.; Carroll, Bobby; Sumpter, Bobby G.; Sokolov, Alexei P.

There are growing experimental evidences showing the existence of an interfacial layer that has a finite thickness with slowing down dynamics in polymer nanocomposites (PNCs). Moreover, it is believed that the interfacial layer plays a significant role on various macroscopic properties of PNCs. A thicker interfacial layer is found to have more pronounced effect on the macroscopic properties such as the mechanical enhancement. However, it is not clear what molecular parameter controls the interfacial layer thickness. Inspired by our recent computer simulations that showed the chain rigidity correlated well with the interfacial layer thickness, we performed systematic experimental studies on different polymer nanocomposites by varying the chain stiffness. Combining small-angle X-ray scattering, broadband dielectric spectroscopy and temperature modulated differential scanning calorimetry, we find a good correlation between the polymer Kuhn length and the thickness of the interfacial layer, confirming the earlier computer simulations results. Our findings provide a direct guidance for the design of new PNCs with desired properties.

Origins of the helical wrapping of phenyleneethynylene polymers about single-walled carbon nanotubes.

PubMed

Von Bargen, Christopher D; MacDermaid, Christopher M; Lee, One-Sun; Deria, Pravas; Therien, Michael J; Saven, Jeffery G

2013-10-24

The highly charged, conjugated polymer poly[p-{2,5-bis(3-propoxysulfonicacidsodiumsalt)}phenylene]ethynylene (PPES) has been shown to wrap single-wall carbon nanotubes (SWNTs), adopting a robust helical superstructure. Surprisingly, PPES adopts a helical rather than a linear conformation when adhered to SWNTs. The complexes formed by PPES and related polymers upon helical wrapping of a SWNT are investigated using atomistic molecular dynamics (MD) simulations in the presence and absence of aqueous solvent. In simulations of the PPES/SWNT system in an aqueous environment, PPES spontaneously takes on a helical conformation. A potential of mean force, ΔA(ξ), is calculated as a function of ξ, the component of the end-to-end vector of the polymer chain projected on the SWNT axis; ξ is a monotonic function of the polymer's helical pitch. ΔA(ξ) provides a means to quantify the relative free energies of helical conformations of the polymer when wrapped about the SWNT. The aqueous system possesses a global minimum in ΔA(ξ) at the experimentally observed value of the helical pitch. The presence of this minimum is associated with preferred side chain conformations, where the side chains adopt conformations that provide van der Waals contact between the tubes and the aliphatic components of the side chains, while exposing the anionic sulfonates for aqueous solvation. The simulations provide a free energy estimate of a 0.2 kcal/mol/monomer preference for the helical over the linear conformation of the PPES/SWNT system in an aqueous environment.

Networks 90: Polymer Networks Group Meeting (10th) and IUPAC international Symposium on Polymer Networks (10th) Held in Jerusalem on 20-25 May 1990. Programme and Abstracts

DTIC Science & Technology

1990-05-25

INCLUDING ORIENTATIONAL INTERACTIONS BETWEEN CHAIN SEGMENTS B. Deloche, E.T. Samulski (France, USA) CHAIN SEGMENT ORDERING IN STRAINED BIMODAL P-2 PDMS...theory of elastomers is difficult because it requires a detailed study of many body interactions . A theory of elasticity must address the following: (1...a Kirchhoff matrix which describes the connectivity of the network (Kc) or the linear chains (Ku). The nonbonded interactions are handled with the

Thermal conductivity of a single polymer chain

NASA Astrophysics Data System (ADS)

Freeman, J. J.; Morgan, G. J.; Cullen, C. A.

1987-05-01

Numerical experiments have been performed with use of a fairly realistic model for polyethylene which has enabled the effects of anharmonicity, temperature, and positional disorder on the thermal conductivity to be investigated. It has been shown that the classical conductivity may be substantially increased by both increasing the strength of the anharmonic forces and by decreasing the chain temperature. Although the conductivity of individual chains is found to be high, realistic values for the conductivity of a bulk material may be understood provided that due account is taken of the polymer conformation and interchain coupling.

The Characterization of Material Properties and Structural Dynamics of the Manduca Sexta Forewing for Application to Flapping Wing Micro Air Vehicle Design

DTIC Science & Technology

2012-09-13

2.1.1 Wing Morphology. Insect wings are formed from a complex makeup of polymer based chains, Chitin , that form the Cuticle, which provides the strong... Chitin , a long-chain polymer and a deriva- tive of glucose, is the main component of the exoskeletons and wings of insects . Due to the ability of the...biological specimen to vary the bonding chains, assemblage of nanofibers, and crystalline structure, the material properties of chitin can vary over a

Electron-deficient triarylborane block copolymers: synthesis by controlled free radical polymerization and application in the detection of fluoride ions.

PubMed

Cheng, Fei; Bonder, Edward M; Jäkle, Frieder

2013-11-20

Luminescent triarylborane homo and block copolymers with well-defined chain architectures were synthesized via reversible addition-fragmentation chain transfer polymerization of a vinyl-functionalized borane monomer. The Lewis acid properties of the polymers were exploited in the luminescent detection of fluoride ions. A dual-responsive fluoride sensor was developed by taking advantage of the reversible self-assembly of a PNIPAM-based amphiphilic block copolymer. Anion detection in aqueous solution was realized by introducing positively charged pyridinium moieties along the polymer chain.

Thiolated quaternary ammonium-chitosan conjugates for enhanced precorneal retention, transcorneal permeation and intraocular absorption of dexamethasone.

PubMed

Zambito, Ylenia; Di Colo, Giacomo

2010-06-01

Previously, a quaternary ammonium (N(+))-chitosan (Ch) conjugate (N(+)(60)-Ch) characterized by short pendant chains, made of 1.7+/-0.1 adjacent diethyl-dimethylene-ammonium groups, substituted onto the primary amino group of the chitosan repeating units (degree of substitution, 59.2+/-4.5%) was used to synthesize a multifunctional non-cytotoxic thiomer (N(+)(60)-Ch-SH(5)), carrying 4.5+/-0.7% thiol-bearing 3-mercaptopropionamide besides quaternary ammonium groups. The present work was aimed at evaluating the potential of N(+)(60)-Ch-SH(5) and N(+)(60)-Ch as bioactive excipients for dexamethasone (DMS) eyedrops. The DMS permeability across excised rabbit cornea was enhanced over the control value by the thiomer and the parent polymer to about the same extent (3.8 vs. 4.1 times). The mean precorneal retention time and AUC in the aqueous of DMS instilled in rabbit eyes via eyedrops were enhanced by the thiomer (MRT=77.96+/-3.57 min, AUC=33.19+/-6.96 microg ml(-1) min) more than the parent polymer (MRT=65.74+/-4.91 min, AUC=21.48+/-3.81 microg ml(-1) min) over the control (MRT=5.07+/-0.25 min, AUC=6.25+/-0.65 microg ml(-1) min). The quaternary ammonium ions were responsible for both permeabilization of corneal epithelium and polymer adhesion to precorneal mucus, while the thiols increased the latter. This synergistic action is the basis of the higher thiomer bioactivity in vivo. A good ocular tolerability of the chitosan derivatives resulted from in vivo experiments. Copyright 2010 Elsevier B.V. All rights reserved.

Shape-Persistent, Thermoresponsive Polypeptide Brushes Prepared by Vapor Deposition Surface-Initiated Ring-Opening Polymerization of α-Amino Acid N -Carboxyanhydrides

DOE PAGES

Shen, Yong; Desseaux, Solenne; Aden, Bethany; ...

2015-04-20

We report that surface-grafting thermoresponsive polymers allows the preparation of thin polymer brush coatings with surface properties that can be manipulated by variation of temperature. In most instances, thermoresponsive polymer brushes are produced using polymers that dehydrate and collapse above a certain temperature. This report presents the preparation and properties of polymer brushes that show thermoresponsive surface properties, yet are shape-persistent in that they do not undergo main chain collapse. The polymer brushes presented here are obtained via vapor deposition surface-initiated ring-opening polymerization (SI-ROP) of γ-di- or tri(ethylene glycol)-modified glutamic acid N-carboxyanhydrides. Vapor deposition SI-ROP of γ-di- or tri(ethylene glycol)-modifiedmore » L- or D-glutamic acid N-carboxyanhydrides affords helical surface-tethered polymer chains that do not show any changes in secondary structure between 10 and 70 °C. QCM-D experiments, however, revealed significant dehydration of poly(γ-(2-(2-methoxyethoxy)ethyl)-l-glutamate) (poly(L-EG 2-Glu)) brushes upon heating from 10 to 40 °C. At the same time, AFM and ellipsometry studies did not reveal significant variations in film thickness over this temperature range, which is consistent with the shape-persistent nature of these polypeptide brushes and indicates that the thermoresponsiveness of the films is primarily due to hydration and dehydration of the oligo(ethylene glycol) side chains. The results we present here illustrate the potential of surface-initiated NCA ring-opening polymerization to generate densely grafted assemblies of polymer chains that possess well-defined secondary structures and tunable surface properties. These polypeptide brushes complement their conformationally unordered counterparts that can be generated via surface-initiated polymerization of vinyl-type monomers and represent another step forward to biomimetic surfaces and interfaces.« less

Release of DNA from polyelectrolyte multilayers fabricated using 'charge-shifting' cationic polymers: tunable temporal control and sequential, multi-agent release.

PubMed

Sun, Bin; Lynn, David M

2010-11-20

We report an approach to the design of multilayered polyelectrolyte thin films (or 'polyelectrolyte multilayers', PEMs) that can be used to provide tunable control over the release of plasmid DNA (or multiple different DNA constructs) from film-coated surfaces. Our approach is based upon methods for the layer-by-layer assembly of DNA-containing thin films, and exploits the properties of a new class of cationic 'charge-shifting' polymers (amine functionalized polymers that undergo gradual changes in net charge upon side chain ester hydrolysis) to provide control over the rates at which these films erode and release DNA. We synthesized two 'charge-shifting' polymers (polymers 1 and 2) containing different side chain structures by ring-opening reactions of poly(2-alkenyl azlactone)s with two different tertiary amine functionalized alcohols (3-dimethylamino-1-propanol and 2-dimethylaminoethanol, respectively). Subsequent characterization revealed large changes in the rates of side chain ester hydrolysis for these two polymers; whereas the half-life for the hydrolysis of the esters in polymer 1 was ~200 days, the half-life for polymer 2 was ~6 days. We demonstrate that these large differences in side chain hydrolysis make possible the design of PEMs that erode and promote the surface-mediated release of DNA either rapidly (e.g., over ~3 days for films fabricated using polymer 2) or slowly (e.g., over ~1 month for films fabricated using polymer 1). We demonstrate further that it is possible to design films with release profiles that are intermediate to these two extremes by fabricating films using solutions containing different mixtures of these two polymers. This approach can thus expand the usefulness of these two polymers and achieve a broader range of DNA release profiles without the need to synthesize polymers with new structures or properties. Finally, we demonstrate that polymers 1 and 2 can be used to fabricate multilayered films with hierarchical structures that promote the sequential release of two different DNA constructs with separate and distinct release profiles (e.g., the release of a first construct over a period of ~3 days, followed by the sustained release of a second for a period of ~70 days). With further development, this approach could contribute to the design of functional thin films and surface coatings that provide sophisticated control over the timing and the order of the release of two or more DNA constructs (or other agents) of interest in a range of biomedical contexts. Copyright © 2010 Elsevier B.V. All rights reserved.

Tunable Assembly of Gold Nanorods in Polymer Solutions To Generate Controlled Nanostructured Materials

DOE Office of Scientific and Technical Information (OSTI.GOV)

Poling-Skutvik, Ryan; Lee, Jonghun; Narayanan, Suresh

In this study, gold nanorods grafted with short chain polymers are assembled into controlled open structures using polymer-induced depletion interactions and structurally characterized using small angle x-ray scattering. When the nanorod diameter is smaller than the radius of gyration of the depletant polymer, the depletion interaction depends solely on the correlation length of the polymer solution and not directly on the polymer molecular weight. As the polymer concentration increases, the stronger depletion interactions increasingly compress the grafted chains and push the gold nanorods closer together. By contrast, other structural characteristics such as the number of nearest neighbors and fractal dimensionmore » exhibit a non-monotonic dependence on polymer concentration. These parameters are maximal at intermediate concentrations, which are attributed to a crossover from reaction-limited to diffusion-limited aggregation. Finally, the control over structural properties of anisotropic nanoscale building blocks demonstrated here will be beneficial to designing and producing materials in situ with specific direction-dependent nanoscale properties and provides a crucial route for advances in additive manufacturing.« less

Tunable Assembly of Gold Nanorods in Polymer Solutions To Generate Controlled Nanostructured Materials

DOE PAGES

Poling-Skutvik, Ryan; Lee, Jonghun; Narayanan, Suresh; ...

2018-01-17

In this study, gold nanorods grafted with short chain polymers are assembled into controlled open structures using polymer-induced depletion interactions and structurally characterized using small angle x-ray scattering. When the nanorod diameter is smaller than the radius of gyration of the depletant polymer, the depletion interaction depends solely on the correlation length of the polymer solution and not directly on the polymer molecular weight. As the polymer concentration increases, the stronger depletion interactions increasingly compress the grafted chains and push the gold nanorods closer together. By contrast, other structural characteristics such as the number of nearest neighbors and fractal dimensionmore » exhibit a non-monotonic dependence on polymer concentration. These parameters are maximal at intermediate concentrations, which are attributed to a crossover from reaction-limited to diffusion-limited aggregation. Finally, the control over structural properties of anisotropic nanoscale building blocks demonstrated here will be beneficial to designing and producing materials in situ with specific direction-dependent nanoscale properties and provides a crucial route for advances in additive manufacturing.« less

Comblike poly(ethylene oxide)/hydrophobic C6 branched chitosan surfactant polymers as anti-infection surface modifying agents.

PubMed

Mai-ngam, Katanchalee

2006-05-01

A series of structurally well-defined poly(ethylene oxide)/hydrophobic C6 branched chitosan surfactant polymers that undergo surface induced self assembly on hydrophobic biomaterial surfaces were synthesized and characterized. The surfactant polymers consist of low molecular weight (Mw) chitosan backbone with hydrophilic poly(ethylene oxide) (PEO) and hydrophobic hexyl pendant groups. Chitosan was depolymerized by nitrous acid deaminative cleavage. Hexanal and aldehyde-terminated PEO chains were simultaneously attached to low Mw chitosan hydrochloride via reductive amination. The surfactant polymers were prepared with various ratios of the two side chains. The molecular composition of the surfactant polymers was determined by FT-IR and 1H NMR. Surface active properties at the air-water interface were determined by Langmuir film balance measurements. The surfactant polymers with PEO/hexyl ratios of 1:3.0 and 1:14.4 were used as surface modifying agents to investigate their anti-infection properties. E. coli adhesion on Silastic surface was decreased significantly by the surfactant polymer with PEO/hexyl 1:3.0. Surface growth of adherent E. coli was effectively suppressed by both tested surfactant polymers.

On the thermodynamic and kinetic investigations of a [c2]daisy chain polymer

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hmadeh, Mohamad; Fang, Lei; Trabolsi, Ali

2010-01-01

We report a variety of [c2]daisy chain molecules which undergo quantitative, efficient, and fully reversible molecular movements upon the addition of base/acid in organic solvents. Such externally triggered molecular movements can induce the contraction and extension of the [c2]daisy chain molecule as a whole. A linear polymer of such a bistable [c2]daisy chain exerts similar types of movements and can be looked upon as a candidate for the development of artificial muscles. The spectrophotometric investigations of both the monomeric and polymeric bistable [c2]daisy chains, as well as the corresponding model compounds, were performed in MeCN at room temperature, in ordermore » to obtain the thermodynamic parameters for these mechanically interlocked molecules. Based on their spectrophotometric and thermodynamic characteristics, kinetic analysis of the acid/base-induced contraction and extension of the [c2]daisy chain monomer and polymer were conducted by employing a stopped-flow technique. These kinetic data suggest that the rates of contraction and extension for these [c2]daisy chain molecules are determined by the thermodynamic stabilities of the corresponding kinetic intermediates. Faster switching rates for both the contraction and extension processes of the polymeric [c2]daisy chain were observed when compared to those of its monomeric counterpart. These kinetic and thermodynamic investigations on [c2]daisy chain-based muscle-like compounds provide important information for those seeking an understanding of the mechanisms of actuation in mechanically interlocked macromolecules.« less

Simulation Studies of LCST-like Phase Transitions in Elastin-like Polypeptides (ELPs) and Conjugates of ELP with Rigid Macromolecules

NASA Astrophysics Data System (ADS)

Condon, Joshua; Martin, Tyler; Jayaraman, Arthi

We use atomistic (AA) and coarse-grained (CG) molecular dynamics simulations to elucidate the thermodynamic driving forces governing lower critical solution temperature (LCST)-like phase transition exhibited by elastin-like peptides (ELPs) and conjugates of ELP with other macromolecules. In the AA simulations, we study ELP oligomers in explicit water, and mark the transition as the temperature at which they undergo a change in ``hydration'' state. While AA simulations are restricted to small systems of short ELPs and do not capture the chain aggregation observed in experiments of ELPs, they guide the phenomenological CG model development by highlighting the solvent induced polymer-polymer effective interactions with changing temperature. In the CG simulations, we capture the LCST polymer aggregation by increasing polymer-polymer effective attractive interactions in an implicit solvent. We examine the impact of conjugating a block of LCST polymer to another rigid unresponsive macromolecular block on the LCST-like transition. We find that when multiple LCST polymers are conjugated to a rigid polymer block, increased crowding of the LCST polymers shifts the onset of chain aggregation to smaller effective polymer-polymer attraction compared to the free LCST polymers. These simulation results provide guidance on the design of conjugated bio-mimetic thermoresponsive materials, and shape the fundamental understanding of the impact of polymer crowding on phase behavior in thermoresponsive LCST polymer systems.

Structural symmetry breaking of silicon containing polymers and their relation with electrical conductivity and Raman active vibrations

NASA Astrophysics Data System (ADS)

Cabrera, Alejandro; González, Carmen; Tagle, Luis; Terraza, Claudio; Volkmann, Ulrich; Barriga, Andrés; Ramos, Esteban; Pavez, Maximiliano

2011-03-01

The incorporation of silicon into the polymeric main chain or side groups can provide an enhancement in chemical, physical and mechanical properties. We report an efficient method for the synthesis of polymers containing silicon in the main chain, from the polycondensation reactions of four optically active carboxylic diacid. The solubility of the polymers, the molecular weight, the glass transition and the thermal stability were studied by standard techniques. Raman spectroscopy was used to probe the conformation of stretching modes as function of the temperature. The conductivity measurements indicated that the alignment of the molecules is a crucial parameter for electrical performance. When the polymers were exposed to iodine, charge transfer increased their mobility and decreased their optical band gaps. These novel properties highlight the possibility to generate alternative active opto-electronics polymers.

New Aptes Cross-linked Polymers from Poly(ethylene oxide)s and Cyanuric Chloride for Lithium Batteries

NASA Technical Reports Server (NTRS)

Tigelaar, Dean M.; Meador, Mary Ann B.; Kinder, James D.; Bennett, William R.

2005-01-01

A new series of polymer electrolytes for use as membranes for lithium batteries are described. Electrolytes were made by polymerization between cyanuric chloride and diamino-terminated poly(ethylene oxide)s, followed by cross-linking via a sol-gel process. Thermal analysis and lithium conductivity of freestanding polymer films were studied. The effects of several variables on conductivity were investigated, such as length of backbone PEO chain, length of branching PEO chain, extent of branching, extent of cross-linking, salt content, and salt counterion. Polymer films with the highest percentage of PEO were found to be the most conductive, with a maximum lithium conductivity of 3.9 x 10(exp -5) S/cm at 25 C. Addition of plasticizer to the dry polymers increased conductivity by an order of magnitude.

Three-Dimensional Polypeptide Architectures Through Tandem Catalysis and Click Chemistry

NASA Astrophysics Data System (ADS)

Rhodes, Allison Jane

Rapid renal clearance, liver accumulation, proteolytic degradation and non-specificity are challenges small molecule drugs, peptides, proteins and nucleic acid therapeutics encounter en route to their intended destination within the body. Nanocarriers (i.e. dendritric polymers, vesicles, and micelles) of approximately 100 nm in diameter, shuttle small molecule drugs to their desired location through passive (EPR effect) and active (ligand-mediated) targeting, maximizing therapeutic efficiency. Polypeptide-based polymers are water-soluble, biocompatible, non-toxic and are therefore excellent candidates for nanocarriers. Dendritic polymers, including dendrimers, cylindrical brushes, and star polymers, are the newest class of nanomedicine drug delivery vehicles. The synthesis and characterization of dendritic polymers is challenging, with tedious and costly procedures. Dendritic polymers possess peripheral pendent functional groups that can potentially be used in ligand-mediated drug delivery vehicles and bioimaging applications. More specifically, cylindrical brushes are dendritic polymers where a single linear polymer (primary chain) has polymer chains (secondary chains) grafted to it. Recently, research groups have shown that cylindrical brush polymers are capable of nanoparticle and supramolecular structure self-assembly. The facile preparation of high-density brush copolypeptides by the "grafting from" approach will be discussed. This approach utilizes a novel, tandem catalytic methodology where alloc-alpha-aminoamide groups are installed within the side-chains of the alpha-amino-N-carboxyanhydride (NCA) monomer serving as masked initiators. These groups are inert during cobalt initiated NCA polymerization, and give alloc-alpha-aminoamide substituted polypeptide main-chains. The alloc-alpha-aminoamide groups are activated in situ using nickel to generate initiators for growth of side-chain brush segments. This method proves to be efficient, yielding well-defined, high-density brushes for applications in drug delivery and imaging. Here, we also report a method for the synthesis of soluble, well-defined, azido functionalized polypeptides in a straightforward, 3-step synthesis. Homo and diblock azidopolypeptides were prepared with controlled segment lengths via living polymerization using Co(PMe3)4 initiator. Through copper azide alkyne click chemistry (CuAAC) in organic solvent, azidopolypeptides were regioselectively and quantitatively modified with carboxylic acid (pH-responsive), amino acid and sugar functional groups. Finally, the advances towards well-defined hyperbranched polypeptides through alpha-amino-acid-N-thiocarboxyanhydrides (NTAs) will be discussed. Within the past 10 years, controlled NCA (alpha-amino acid-N-carboxyanhydride) ring-opening polymerization (ROP) has emerged, expanding the application of copolypeptide polymers in various drug delivery and tissue engineering motifs. Modification of NCA monomers to the corresponding alpha-amino-acid-N-thiocarboxyanhydride (NTA) will diversify ROP reactions, leading to more complex polypeptides (such as hyperbranched polymers), in addition to the possibility of performing these polymerizations under ambient conditions, which would greatly expand their potential utility. The project focuses on the preparation of hyperbranched polypeptides with well-defined architectures and controlled branching density in a one-pot reaction. This will be accomplished by taking advantage of the different selectivities of Co(PMe3)4 and depeNi(COD) polymerization initiators, and by exploiting the reactivity difference between NCA and the more stable NTA monomers.

DNA-Templated Polymerization of Side-Chain-Functionalized Peptide Nucleic Acid Aldehydes

PubMed Central

Kleiner, Ralph E.; Brudno, Yevgeny; Birnbaum, Michael E.; Liu, David R.

2009-01-01

The DNA-templated polymerization of synthetic building blocks provides a potential route to the laboratory evolution of sequence-defined polymers with structures and properties not necessarily limited to those of natural biopolymers. We previously reported the efficient and sequence-specific DNA-templated polymerization of peptide nucleic acid (PNA) aldehydes. Here, we report the enzyme-free, DNA-templated polymerization of side-chain-functionalized PNA tetramer and pentamer aldehydes. We observed that the polymerization of tetramer and pentamer PNA building blocks with a single lysine-based side chain at various positions in the building block could proceed efficiently and sequence-specifically. In addition, DNA-templated polymerization also proceeded efficiently and in a sequence-specific manner with pentamer PNA aldehydes containing two or three lysine side chains in a single building block to generate more densely functionalized polymers. To further our understanding of side-chain compatibility and expand the capabilities of this system, we also examined the polymerization efficiencies of 20 pentamer building blocks each containing one of five different side-chain groups and four different side-chain regio- and stereochemistries. Polymerization reactions were efficient for all five different side-chain groups and for three of the four combinations of side-chain regio- and stereochemistries. Differences in the efficiency and initial rate of polymerization correlate with the apparent melting temperature of each building block, which is dependent on side-chain regio- and stereochemistry, but relatively insensitive to side-chain structure among the substrates tested. Our findings represent a significant step towards the evolution of sequence-defined synthetic polymers and also demonstrate that enzyme-free nucleic acid-templated polymerization can occur efficiently using substrates with a wide range of side-chain structures, functionalization positions within each building block, and functionalization densities. PMID:18341334

Phase separation of comb polymer nanocomposite melts.

PubMed

Xu, Qinzhi; Feng, Yancong; Chen, Lan

2016-02-07

In this work, the spinodal phase demixing of branched comb polymer nanocomposite (PNC) melts is systematically investigated using the polymer reference interaction site model (PRISM) theory. To verify the reliability of the present method in characterizing the phase behavior of comb PNCs, the intermolecular correlation functions of the system for nonzero particle volume fractions are compared with our molecular dynamics simulation data. After verifying the model and discussing the structure of the comb PNCs in the dilute nanoparticle limit, the interference among the side chain number, side chain length, nanoparticle-monomer size ratio and attractive interactions between the comb polymer and nanoparticles in spinodal demixing curves is analyzed and discussed in detail. The results predict two kinds of distinct phase separation behaviors. One is called classic fluid phase boundary, which is mediated by the entropic depletion attraction and contact aggregation of nanoparticles at relatively low nanoparticle-monomer attraction strength. The second demixing transition occurs at relatively high attraction strength and involves the formation of an equilibrium physical network phase with local bridging of nanoparticles. The phase boundaries are found to be sensitive to the side chain number, side chain length, nanoparticle-monomer size ratio and attractive interactions. As the side chain length is fixed, the side chain number has a large effect on the phase behavior of comb PNCs; with increasing side chain number, the miscibility window first widens and then shrinks. When the side chain number is lower than a threshold value, the phase boundaries undergo a process from enlarging the miscibility window to narrowing as side chain length increases. Once the side chain number overtakes this threshold value, the phase boundary shifts towards less miscibility. With increasing nanoparticle-monomer size ratio, a crossover of particle size occurs, above which the phase separation is consistent with that of chain PNCs. The miscibility window for this condition gradually narrows while the other parameters of the PNCs system are held constant. These results indicate that the present PRISM theory can give molecular-level details of the underlying mechanisms of the comb PNCs. It is hoped that the results can be used to provide useful guidance for the future design control of novel, thermodynamically stable comb PNCs.

Effect of Nanoparticle Core Size on Polymer-Coated Gold Nanoparticle Location in Block Copolymers

NASA Astrophysics Data System (ADS)

Petrie, J. D.; Fredrickson, G. H.; Kramer, E. J.

2009-03-01

Gold nanoparticles modified by short chain polymer thiols [Au-PS] can be designed to strongly localize either in the PS domains of a polystyrene-b-poly(2-vinylpyridine) [PS-PVP] block copolymer or at the interface. The P2VP block has a stronger attractive interaction with bare gold than the PS block. Thus, when the areal chain density σ of end-attached PS chains falls below a critical areal chain density σc the Au-PS nanoparticles adsorb to the PS-b-P2VP interface. The effect of the polymer ligand molecular weight on the σc has been shown to scale as σc˜ ((R + Rg)/(R*Rg))̂2, where R is the curvature of the Au nanoparticle core radius. To test this scaling relation for σc further we are synthesizing gold nanoparticles with different core radii and will present preliminary results on σc as a function of R.

Effect of Ligand Molecular Weight and Nanoparticle Core Size on Polymer-Coated Gold Nanoparticle Location in Block Copolymers

NASA Astrophysics Data System (ADS)

Petrie, Joshua; Kim, Bumjoon; Fredrickson, Glenn; Kramer, Ed

2008-03-01

Gold nanoparticles modified by short chain polymer thiols [Au-PS] can be designed to strongly localize in either domain of a polystyrene-b-poly(2-vinylpyridine) [PS-PVP] block copolymer or at the interface. The P2VP block has a stronger attractive interaction with bare gold than the PS block. Thus, when the areal chain density σ of end-attached PS chains falls below a critical areal chain density σc the Au-PS nanoparticles adsorb to the PS-b-P2VP interface. The effect of the polymer ligand molecular weight on the σchas been shown to scale as σc˜ ((R+Rg)/(R*Rg))̂2, where R is the curvature of the Au nanoparticle core radius. To test this scaling relation for σc further we are synthesizing gold nanoparticles with different core radii and will present preliminary results on σcas a function of R.

Primitive Path Analysis and Stress Distribution in Highly Strained Macromolecules

PubMed Central

2017-01-01

Polymer material properties are strongly affected by entanglement effects. For long polymer chains and composite materials, they are expected to be at the origin of many technically important phenomena, such as shear thinning or the Mullins effect, which microscopically can be related to topological constraints between chains. Starting from fully equilibrated highly entangled polymer melts, we investigate the effect of isochoric elongation on the entanglement structure and force distribution of such systems. Theoretically, the related viscoelastic response usually is discussed in terms of the tube model. We relate stress relaxation in the linear and nonlinear viscoelastic regimes to a primitive path analysis (PPA) and show that tension forces both along the original paths and along primitive paths, that is, the backbone of the tube, in the stretching direction correspond to each other. Unlike homogeneous relaxation along the chain contour, the PPA reveals a so far not observed long-lived clustering of topological constraints along the chains in the deformed state. PMID:29503762

Mass spectrometric method to determine the chain length of oligosaccharides attached to phenolic polymers by nonglycosidic linkages

Treesearch

James L. Minor; Roger C. Pettersen

1987-01-01

In many plants, a portion of the polysaccharides appears to have a very low degree of cross-linking with aromatic polymers such as lignin or flavolans. The proportion of cross-linked units may be enriched for study by enzymatically hydrolyzing the nonbonded carbohydrates. A convenient method is described for the simultaneous analysis of sugar content and apparent chain...

Accessing conjugated polymers with precisely controlled heterobisfunctional chain ends via post-polymerization modification of the OTf group and controlled Pd(0)/t-Bu 3P-catalyzed Suzuki cross-coupling polymerization

DOE PAGES

Hu, Qiao -Sheng; Hong, Kunlun; Zhang, Hong -Hai

2015-08-12

In this study, a general strategy toward the synthesis of well-defined conjugated polymers with controlled heterobisfunctional chain ends via combination of controlled Pd(0)/t-Bu 3P Suzuki cross-coupling polymerization with the post-polymerization modification of the triflate (OTf) group was disclosed.

The Dependence of Strength in Plastics upon Polymer Chain Length and Chain Orientation: An Experiment Emphasizing the Statistical Handling and Evaluation of Data.

ERIC Educational Resources Information Center

Spencer, R. Donald

1984-01-01

Describes an experiment (using plastic bags) designed to give students practical understanding on using statistics to evaluate data and how statistical treatment of experimental results can enhance their value in solving scientific problems. Students also gain insight into the orientation and structure of polymers by examining the plastic bags.…

Accessing conjugated polymers with precisely controlled heterobisfunctional chain ends via post-polymerization modification of the OTf group and controlled Pd(0)/t-Bu 3P-catalyzed Suzuki cross-coupling polymerization

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hu, Qiao -Sheng; Hong, Kunlun; Zhang, Hong -Hai

In this study, a general strategy toward the synthesis of well-defined conjugated polymers with controlled heterobisfunctional chain ends via combination of controlled Pd(0)/t-Bu 3P Suzuki cross-coupling polymerization with the post-polymerization modification of the triflate (OTf) group was disclosed.

Effect of chain rigidity on network architecture and deformation behavior of glassy polymer networks

NASA Astrophysics Data System (ADS)

Knowles, Kyler Reser

Processing carbon fiber composite laminates creates molecular-level strains in the thermoset matrix upon curing and cooling which can lead to failures such as geometry deformations, micro-cracking, and other issues. It is known strain creation is attributed to the significant volume and physical state changes undergone by the polymer matrix throughout the curing process, though storage and relaxation of cure-induced strains remain poorly understood. This dissertation establishes two approaches to address the issue. The first establishes testing methods to simultaneously measure key volumetric properties of a carbon fiber composite laminate and its polymer matrix. The second approach considers the rigidity of the polymer matrix in regards to strain storage and relaxation mechanisms which ultimately control composite performance throughout manufacturing and use. Through the use of a non-contact, full-field strain measurement technique known as digital image correlation (DIC), we describe and implement useful experiments which quantify matrix and composite parameters necessary for simulation efforts and failure models. The methods are compared to more traditional techniques and show excellent correlation. Further, we established relationships which represent matrix-fiber compatibility in regards to critical processing constraints. The second approach involves a systematic study of epoxy-amine networks which are chemically-similar but differ in chain segment rigidity. Prior research has investigated the isomer effect of glassy polymers, showing sizeable differences in thermal, volumetric, physical, and mechanical properties. This work builds on these themes and shows the apparent isomer effect is rather an effect of chain rigidity. Indeed, it was found that structurally-dissimilar polymer networks exhibit very similar properties as a consequence of their shared average network rigidity. Differences in chain packing, as a consequence of chain rigidity, were shown to alter the physical, volumetric, and mechanical properties of the glassy networks. Chain rigidity was found to directly control deformation mechanisms, which were related to the yielding behavior of the epoxy network series. The unique benefit to our approach is the ability to separate the role of rigidity - an intramolecular parameter - from intermolecular phenomena which otherwise influence network properties.

Structure and Dynamics of Interacting Nanoparticles in Semidilute Polymer Solutions

DOE PAGES

Pollng-Skutvik, Ryan; Mongcopa, Katrina Irene S.; Faraone, Antonio; ...

2016-08-17

We investigate the structure and dynamics of silica nanoparticles and polymer chains in semidilute solutions of high molecular weight polystyrene in 2-butanone to determine the effect of long-range interparticle interactions on the coupling between particle and polymer dynamics. Particles at concentrations of 1–10 wt % are well dispersed in the semidilute polymer solutions and exhibit long-range electrostatic repulsions between particles. Because the particles are comparably sized to the radius of gyration of the polymer, the particle dynamics is predicted to couple to that of the polymer. We verify that the polymer structure and dynamics are not significantly affected by themore » particles, indicating that the particle–polymer coupling does not change with increasing particle loading. We find that the coupling between the dynamics of comparably sized particles and polymer results in subdiffusive particle dynamics, as expected. Over the interparticle distance, however, the particle dynamics is hindered and not fully described by the relaxation of the surrounding polymer chains. Instead, the particle dynamics is inversely related to the structure factor, suggesting that physical particle–polymer coupling on short length scales and interparticle interactions on long length scales both present energetic barriers to particle motion that lead to subdiffusive dynamics and de Gennes narrowing, respectively.« less

Block and Graft Copolymers of Polyhydroxyalkanoates

NASA Astrophysics Data System (ADS)

Marchessault, Robert H.; Ravenelle, François; Kawada, Jumpei

2004-03-01

Polyhydroxyalkanoates (PHAs) were modified for diblock copolymer and graft polymer by catalyzed transesterification in the melt and by chemical synthesis to extend the side chains of the PHAs, and the polymers were studied by transmission electron microscopy (TEM) X-ray diffraction, thermal analysis and nuclear magnetic resonance (NMR). Catalyzed transesterification in the melt is used to produce diblock copolymers of poly[3-hydroxybutyrate] (PHB) and monomethoxy poly[ethylene glycol] (mPEG) in a one-step process. The resulting diblock copolymers are amphiphilic and self-assemble into sterically stabilized colloidal suspensions of PHB crystalline lamellae. Graft polymer was synthesized in a two-step chemical synthesis from biosynthesized poly[3-hydroxyoctanoate-co-3-hydroxyundecenoate] (PHOU) containing ca. 25 mol chains. 11-mercaptoundecanoic acid reacts with the side chain alkenes of PHOU by the radical addition creating thioether linkage with terminal carboxyl functionalities. The latter groups were subsequently transformed into the amide or ester linkage by tridecylamine or octadecanol, respectively, producing new graft polymers. The polymers have different physical properties than poly[3-hydroxyoctanoate] (PHO) which is the main component of the PHOU, such as non-stickiness and higher thermal stability. The combination of biosynthesis and chemical synthesis produces a hybrid thermoplastic elastomer with partial biodegradability.

Facile Fabrication of Hierarchically Thermoresponsive Binary Polymer Pattern for Controlled Cell Adhesion.

PubMed

Hou, Jianwen; Cui, Lele; Chen, Runhai; Xu, Xiaodong; Chen, Jiayue; Yin, Ligang; Liu, Jingchuan; Shi, Qiang; Yin, Jinghua

2018-03-01

A versatile platform allowing capture and detection of normal and dysfunctional cells on the same patterned surface is important for accessing the cellular mechanism, developing diagnostic assays, and implementing therapy. Here, an original and effective method for fabricating binary polymer brushes pattern is developed for controlled cell adhesion. The binary polymer brushes pattern, composed of poly(N-isopropylacrylamide) (PNIPAAm) and poly[poly(ethylene glycol) methyl ether methacrylate] (POEGMA) chains, is simply obtained via a combination of surface-initiated photopolymerization and surface-activated free radical polymerization. This method is unique in that it does not utilize any protecting groups or procedures of backfilling with immobilized initiator. It is demonstrated that the precise and well-defined binary polymer patterns with high resolution are fabricated using this facile method. PNIPAAm chains capture and release cells by thermoresponsiveness, while POEGMA chains possess high capability to capture dysfunctional cells specifically, inducing a switch of normal red blood cells (RBCs) arrays to hemolytic RBCs arrays on the pattern with temperature. This novel platform composed of binary polymer brush pattern is smart and versatile, which opens up pathways to potential applications as microsensors, biochips, and bioassays. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Effect of Charge Patterning on the Phase Behavior of Polymer Coacervates for Charge Driven Self Assembly

NASA Astrophysics Data System (ADS)

Radhakrishna, Mithun; Sing, Charles E.

Oppositely charged polymers can undergo associative liquid-liquid phase separation when mixed under suitable conditions of ionic strength, temperature and pH to form what are known as `polymeric complex coacervates'. Polymer coacervates find use in diverse array of applications like microencapsulation, drug delivery, membrane filtration and underwater adhesives. The similarity between complex coacervate environments and those in biological systems has also found relevance in areas of bio-mimicry. Our previous works have demonstrated how local charge correlations and molecular connectivity can drastically affect the phase behavior of coacervates. The precise location of charges along the chain therefore dramatically influences the local charge correlations, which consequently influences the phase behavior of coacervates. We investigate the effect of charge patterning along the polymer chain on the phase behavior of coacervates in the framework of the Restricted Primitive Model using Gibbs Ensemble Monte Carlo simulations. Our results show that charge patterning dramatically changes the phase behavior of polymer coacervates, which contrasts with the predictions of the classical Voorn-Overbeek theory. This provides the basis for designing new materials through charge driven self assembly by controlling the positioning of the charged monomers along the chain.

Functionalization of multi-walled carbon nanotubes by epoxide ring-opening polymerization

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jin Fanlong; Rhee, Kyong Yop; Park, Soo-Jin, E-mail: sjpark@inha.ac.kr

2011-12-15

In this study, covalent functionalization of carbon nanotubes (CNTs) was accomplished by surface-initiated epoxide ring-opening polymerization. FT-IR spectra showed that polyether and epoxide group covalently attached to the sidewalls of CNTs. TGA results indicated that the polyether was successfully grown from the CNT surface, with the final products having a polymer weight percentage of ca. 14-74 wt%. The O/C ratio of CNTs increased significantly from 5.1% to 29.8% after surface functionalization of CNTs. SEM and TEM images of functionalized CNTs exhibited that the tubes were enwrapped by polymer chains with thickness of several nanometers, forming core-shell structures with CNTs atmore » the center. - Graphical abstract: Functionalized CNTs were enwrapped by polymer chains with thickness of several nanometers, forming core-shell structures with CNTs at the center. Highlights: Black-Right-Pointing-Pointer CNTs were functionalized by epoxide ring-opening polymerization. Black-Right-Pointing-Pointer Polyether and epoxide group covalently attached to the sidewalls of CNTs. Black-Right-Pointing-Pointer Functionalized CNTs have a polymer weight percentage of ca. 14-74 wt%. Black-Right-Pointing-Pointer Functionalized CNTs were enwrapped by polymer chains with thickness of several nanometers.« less

Mass dependence of the activation enthalpy and entropy of unentangled linear alkane chains

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jeong, Cheol; Douglas, Jack F.

2015-10-14

The mass scaling of the self-diffusion coefficient D of polymers in the liquid state, D ∼ M{sup β}, is one of the most basic characteristics of these complex fluids. Although traditional theories such as the Rouse and reptation models of unentangled and entangled polymer melts, respectively, predict that β is constant, this exponent for alkanes has been estimated experimentally to vary from −1.8 to −2.7 upon cooling. Significantly, β changes with temperature T under conditions where the chains are not entangled and at temperatures far above the glass transition temperature T{sub g} where dynamic heterogeneity does not complicate the descriptionmore » of the liquid dynamics. Based on atomistic molecular dynamics simulations on unentangled linear alkanes in the melt, we find that the variation of β with T can be directly attributed to the dependence of the enthalpy ΔH{sub a} and entropy ΔS{sub a} of activation on the number of alkane backbone carbon atoms, n. In addition, we find a sharp change in the melt dynamics near a “critical” chain length, n ≈ 17. A close examination of this phenomenon indicates that a “buckling transition” from rod-like to coiled chain configurations occurs at this characteristic chain length and distinct entropy-enthalpy compensation relations, ΔS{sub a} ∝ ΔH{sub a}, hold on either side of this polymer conformational transition. We conclude that the activation free energy parameters exert a significant influence on the dynamics of polymer melts that is not anticipated by either the Rouse and reptation models. In addition to changes of ΔH{sub a} and ΔS{sub a} with M, we expect changes in these free energy parameters to be crucial for understanding the dynamics of polymer blends, nanocomposites, and confined polymers because of changes of the fluid free energy by interfacial interactions and geometrical confinement.« less

Investigation of structure-property relationships in systematic series of novel polymers

NASA Technical Reports Server (NTRS)

Gillham, J. K.

1976-01-01

Solid state transitions in polymeric materials was associated with the onset of sub-molecular motions of the polymer chains. Although these were considered to be intramolecular in general, the local environment of the polymer molecule exerts a strong influence through, for example, the effects of crystallinity, polarity and diluents. The manner of specimen preparation and previous history also affect transitions. The transitions are considered to arise when sufficient free volume is available to permit the occurrence of these side chain and backbone reorientations. The glass transition is the principal transition of amorphous polymeric materials and is associated with the onset of long range segmental motion of the polymer backbone. The various types of shorter range motion occurring below the glass transition have been catalogued.

Effect of chain stiffness on the structure of single-chain polymer nanoparticles

NASA Astrophysics Data System (ADS)

Moreno, Angel J.; Bacova, Petra; Lo Verso, Federica; Arbe, Arantxa; Colmenero, Juan; Pomposo, José A.

2018-01-01

Polymeric single-chain nanoparticles (SCNPs) are soft nano-objects synthesized by purely intramolecular cross-linking of single polymer chains. By means of computer simulations, we investigate the conformational properties of SCNPs as a function of the bending stiffness of their linear polymer precursors. We investigate a broad range of characteristic ratios from the fully flexible case to those typical of bulky synthetic polymers. Increasing stiffness hinders bonding of groups separated by short contour distances and increases looping over longer distances, leading to more compact nanoparticles with a structure of highly interconnected loops. This feature is reflected in a crossover in the scaling behaviour of several structural observables. The scaling exponents change from those characteristic for Gaussian chains or rings in θ-solvents in the fully flexible limit, to values resembling fractal or ‘crumpled’ globular behaviour for very stiff SCNPs. We characterize domains in the SCNPs. These are weakly deformable regions that can be seen as disordered analogues of domains in disordered proteins. Increasing stiffness leads to bigger and less deformable domains. Surprisingly, the scaling behaviour of the domains is in all cases similar to that of Gaussian chains or rings, irrespective of the stiffness and degree of cross-linking. It is the spatial arrangement of the domains which determines the global structure of the SCNP (sparse Gaussian-like object or crumpled globule). Since intramolecular stiffness can be varied through the specific chemistry of the precursor or by introducing bulky side groups in its backbone, our results propose a new strategy to tune the global structure of SCNPs.

Mechanism of the dielectric enhancement in polymer-alumina nano-particle composites

NASA Astrophysics Data System (ADS)

Jacob, Rebecca; Jacob, Anne Pavitra; Mainwaring, David E.

2009-09-01

Polymer-alumina nano-composites with enhanced dielectric properties as a possibility to enable the miniaturization of devices have been reported. The enhancement of dielectric properties was found to be unique to the polymer. In the present work, the mechanism of the dielectric enhancement is established by performing ab initio molecular orbital calculations in order to study the molecular interactions in the interfacial region between the alumina-nano-particle surface and the polymer medium. The calculations predict the existence of strong electrostatic attraction between the positive charge on the aluminium of the alumina clusters and the negative charge of the oxygens of the polymer at the polymer-nano-particle interface resulting in an increase in the dipole moment and the polarization of the system leading to enhanced dielectric properties. The oxygen thus plays a dual role by involving in covalent bonding with the polymer chain and electrostatic bonding interactions with the alumina nano-particles. The unique structure of the polymer provides the highly electronegative oxygens, as carbonyl groups or ether linkages in conjugation with aromatic rings in an extended polymer chain system, facilitating this type of bonding at the interface.

Effects of the internal friction and the solvent quality on the dynamics of a polymer chain closure.

PubMed

Yu, Wancheng; Luo, Kaifu

2015-03-28

Using 3D Langevin dynamics simulations, we investigate the effects of the internal friction and the solvent quality on the dynamics of a polymer chain closure. We show that the chain closure in good solvents is a purely diffusive process. By extrapolation to zero solvent viscosity, we find that the internal friction of a chain plays a non-ignorable role in the dynamics of the chain closure. When the solvent quality changes from good to poor, the mean closure time τc decreases by about 1 order of magnitude for the chain length 20 ≤ N ≤ 100. Furthermore, τc has a minimum as a function of the solvent quality. With increasing the chain length N, the minimum of τc occurs at a better solvent. Finally, the single exponential distributions of the closure time in poor solvents suggest that the negative excluded volume of segments does not alter the nearly Poisson statistical characteristics of the process of the chain closure.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Youm, Sang Gil; Hwang, Euiyong; Chavez, Carlos A.

The ability to control nanoscale morphology and molecular organization in organic semiconducting polymer thin films is an important prerequisite for enhancing the efficiency of organic thin-film devices including organic light-emitting and photovoltaic devices. The current “top-down” paradigm for making such devices is based on utilizing solution-based processing (e.g., spin-casting) of soluble semiconducting polymers. This approach typically provides only modest control over nanoscale molecular organization and polymer chain alignment. A promising alternative to using solutions of presynthesized semiconducting polymers pursues instead a “bottom-up” approach to prepare surface-grafted semiconducting polymer thin films by surface-initiated polymerization of small-molecule monomers. Herein, we describe themore » development of an efficient method to prepare polythiophene thin films utilizing surface-initiated Kumada catalyst transfer polymerization. In this study, we provided evidence that the surface-initiated polymerization occurs by the highly robust controlled (quasi-“living”) chain-growth mechanism. Further optimization of this method enabled reliable preparation of polythiophene thin films with thickness up to 100 nm. Extensive structural studies of the resulting thin films using X-ray and neutron scattering methods as well as ultraviolet photoemission spectroscopy revealed detailed information on molecular organization and the bulk morphology of the films, and enabled further optimization of the polymerization protocol. One of the remarkable findings was that surface-initiated polymerization delivers polymer thin films showing complex molecular organization, where polythiophene chains assemble into lateral crystalline domains of about 3.2 nm size, with individual polymer chains folded to form in-plane aligned and densely packed oligomeric segments (7-8 thiophene units per each segment) within each domain. Achieving such a complex mesoscale organization is virtually impossible with traditional methods relying on solution processing of presynthesized polymers. Another significant advantage of surface-confined polymer thin films is their remarkable stability toward organic solvents and other processing conditions. In addition to controlled bulk morphology, uniform molecular organization, and stability, a unique feature of the surface-initiated polymerization is that it can be used for the preparation of large-area uniformly nanopatterned polymer thin films. Lastly, this was demonstrated using a combination of particle lithography and surface-initiated polymerization. In general, surface-initiated polymerization is not limited to polythiophene but can be also expanded toward other classes of semiconducting polymers and copolymers.« less

Polythiophene thin films by surface-initiated polymerization: Mechanistic and structural studies

DOE PAGES

Youm, Sang Gil; Hwang, Euiyong; Chavez, Carlos A.; ...

2016-06-15

The ability to control nanoscale morphology and molecular organization in organic semiconducting polymer thin films is an important prerequisite for enhancing the efficiency of organic thin-film devices including organic light-emitting and photovoltaic devices. The current “top-down” paradigm for making such devices is based on utilizing solution-based processing (e.g., spin-casting) of soluble semiconducting polymers. This approach typically provides only modest control over nanoscale molecular organization and polymer chain alignment. A promising alternative to using solutions of presynthesized semiconducting polymers pursues instead a “bottom-up” approach to prepare surface-grafted semiconducting polymer thin films by surface-initiated polymerization of small-molecule monomers. Herein, we describe themore » development of an efficient method to prepare polythiophene thin films utilizing surface-initiated Kumada catalyst transfer polymerization. In this study, we provided evidence that the surface-initiated polymerization occurs by the highly robust controlled (quasi-“living”) chain-growth mechanism. Further optimization of this method enabled reliable preparation of polythiophene thin films with thickness up to 100 nm. Extensive structural studies of the resulting thin films using X-ray and neutron scattering methods as well as ultraviolet photoemission spectroscopy revealed detailed information on molecular organization and the bulk morphology of the films, and enabled further optimization of the polymerization protocol. One of the remarkable findings was that surface-initiated polymerization delivers polymer thin films showing complex molecular organization, where polythiophene chains assemble into lateral crystalline domains of about 3.2 nm size, with individual polymer chains folded to form in-plane aligned and densely packed oligomeric segments (7-8 thiophene units per each segment) within each domain. Achieving such a complex mesoscale organization is virtually impossible with traditional methods relying on solution processing of presynthesized polymers. Another significant advantage of surface-confined polymer thin films is their remarkable stability toward organic solvents and other processing conditions. In addition to controlled bulk morphology, uniform molecular organization, and stability, a unique feature of the surface-initiated polymerization is that it can be used for the preparation of large-area uniformly nanopatterned polymer thin films. Lastly, this was demonstrated using a combination of particle lithography and surface-initiated polymerization. In general, surface-initiated polymerization is not limited to polythiophene but can be also expanded toward other classes of semiconducting polymers and copolymers.« less

Tuning the mechanical properties of graphene oxide paper and its associated polymer nanocomposites by controlling cooperative intersheet hydrogen bonding.

PubMed

Compton, Owen C; Cranford, Steven W; Putz, Karl W; An, Zhi; Brinson, L Catherine; Buehler, Markus J; Nguyen, SonBinh T

2012-03-27

The mechanical properties of pristine graphene oxide paper and paper-like films of polyvinyl alcohol (PVA)-graphene oxide nanocomposite are investigated in a joint experimental-theoretical and computational study. In combination, these studies reveal a delicate relationship between the stiffness of these papers and the water content in their lamellar structures. ReaxFF-based molecular dynamics (MD) simulations elucidate the role of water molecules in modifying the mechanical properties of both pristine and nanocomposite graphene oxide papers, as bridge-forming water molecules between adjacent layers in the paper structure enhance stress transfer by means of a cooperative hydrogen-bonding network. For graphene oxide paper at an optimal concentration of ~5 wt % water, the degree of cooperative hydrogen bonding within the network comprising adjacent nanosheets and water molecules was found to optimally enhance the modulus of the paper without saturating the gallery space. Introducing PVA chains into the gallery space further enhances the cooperativity of this hydrogen-bonding network, in a manner similar to that found in natural biomaterials, resulting in increased stiffness of the composite. No optimal water concentration could be found for the PVA-graphene oxide nanocomposite papers, as dehydration of these structures continually enhances stiffness until a final water content of ~7 wt % (additional water cannot be removed from the system even after 12 h of annealing). © 2011 American Chemical Society

The Construction and Validation of All-Atom Bulk-Phase Models of Amorphous Polymers Using the TIGER2/TIGER3 Empirical Sampling Method

PubMed Central

Li, Xianfeng; Murthy, Sanjeeva; Latour, Robert A.

2011-01-01

A new empirical sampling method termed “temperature intervals with global exchange of replicas and reduced radii” (TIGER3) is presented and demonstrated to efficiently equilibrate entangled long-chain molecular systems such as amorphous polymers. The TIGER3 algorithm is a replica exchange method in which simulations are run in parallel over a range of temperature levels at and above a designated baseline temperature. The replicas sampled at temperature levels above the baseline are run through a series of cycles with each cycle containing four stages – heating, sampling, quenching, and temperature level reassignment. The method allows chain segments to pass through one another at elevated temperature levels during the sampling stage by reducing the van der Waals radii of the atoms, thus eliminating chain entanglement problems. Atomic radii are then returned to their regular values and re-equilibrated at elevated temperature prior to quenching to the baseline temperature. Following quenching, replicas are compared using a Metropolis Monte Carlo exchange process for the construction of an approximate Boltzmann-weighted ensemble of states and then reassigned to the elevated temperature levels for additional sampling. Further system equilibration is performed by periodic implementation of the previously developed TIGER2 algorithm between cycles of TIGER3, which applies thermal cycling without radii reduction. When coupled with a coarse-grained modeling approach, the combined TIGER2/TIGER3 algorithm yields fast equilibration of bulk-phase models of amorphous polymer, even for polymers with complex, highly branched structures. The developed method was tested by modeling the polyethylene melt. The calculated properties of chain conformation and chain segment packing agreed well with published data. The method was also applied to generate equilibrated structural models of three increasingly complex amorphous polymer systems: poly(methyl methacrylate), poly(butyl methacrylate), and DTB-succinate copolymer. Calculated glass transition temperature (Tg) and structural parameter profile (S(q)) for each resulting polymer model were found to be in close agreement with experimental Tg values and structural measurements obtained by x-ray diffraction, thus validating that the developed methods provide realistic models of amorphous polymer structure. PMID:21769156

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

PubMed Central

2017-01-01

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

Transient response of nonlinear polymer networks: A kinetic theory

NASA Astrophysics Data System (ADS)

Vernerey, Franck J.

2018-06-01

Dynamic networks are found in a majority of natural materials, but also in engineering materials, such as entangled polymers and physically cross-linked gels. Owing to their transient bond dynamics, these networks display a rich class of behaviors, from elasticity, rheology, self-healing, or growth. Although classical theories in rheology and mechanics have enabled us to characterize these materials, there is still a gap in our understanding on how individuals (i.e., the mechanics of each building blocks and its connection with others) affect the emerging response of the network. In this work, we introduce an alternative way to think about these networks from a statistical point of view. More specifically, a network is seen as a collection of individual polymer chains connected by weak bonds that can associate and dissociate over time. From the knowledge of these individual chains (elasticity, transient attachment, and detachment events), we construct a statistical description of the population and derive an evolution equation of their distribution based on applied deformation and their local interactions. We specifically concentrate on nonlinear elastic response that follows from the strain stiffening response of individual chains of finite size. Upon appropriate averaging operations and using a mean field approximation, we show that the distribution can be replaced by a so-called chain distribution tensor that is used to determine important macroscopic measures such as stress, energy storage and dissipation in the network. Prediction of the kinetic theory are then explored against known experimental measurement of polymer responses under uniaxial loading. It is found that even under the simplest assumptions of force-independent chain kinetics, the model is able to reproduce complex time-dependent behaviors of rubber and self-healing supramolecular polymers.

Adhesion at Entangled Polymer Interfaces: A Unified Approach..

NASA Astrophysics Data System (ADS)

Wool, Richard

2006-03-01

A unified theory of fracture of polymer interfaces was developed which was based on the Rigidity Percolation model of fracture [R.P. Wool, J.Polym.Sci. Part A: Polym Phys., 43,168(2005)]. The polymer fractured critically when the normalized entanglement density p, approached the percolation threshold pc. The fracture energy was found to be G1c ˜ [p-pc]. When applied to interfaces of width X, containing an areal density σ of chains, each contributing L chain entanglements, the percolation term p ˜ σL/X and the percolation threshold was related to σc, Lc, or Xc. For welding of A/A symmetric interfaces, p = σL/X, and pc Lc/M 0, such that when σ/X ˜1/M for randomly distributed chain ends, p˜L ˜ (t/M)^1/2, G/G* = (t/τ*)^1/2, where the weld time τ* ˜ M. When the chain ends are segregated to the surface, σ is constant with time and G/G* = [t/τ*]^1/4. For sub-Tg welding, there exists a surface mobile layer (due to the critical Lindemann Atom fraction) of depth X ˜ 1/δT^ν such that G ˜ δT-2ν, where the critical exponent v = 0.8. For incompatible A/B interfaces of Helfand width d, normalized width w = d/Rge, and entanglement density Nent ˜ d/Le, p ˜ d such that, G1c ˜ [d-dc], G1c ˜ [w-1], and G ˜ [Nent-Nc]. For incompatible A/B interfaces reinforced by an areal density σ of compatibilizer chains, L and X are constant, p ˜ σ, pc ˜σc, such that G1c ˜ [σ-σc], which is in excellent agreement with experimental data.

Side Chain Engineering on Medium Bandgap Copolymers to Suppress Triplet Formation for High-Efficiency Polymer Solar Cells.

PubMed

Xue, Lingwei; Yang, Yankang; Xu, Jianqiu; Zhang, Chunfeng; Bin, Haijun; Zhang, Zhi-Guo; Qiu, Beibei; Li, Xiaojun; Sun, Chenkai; Gao, Liang; Yao, Jia; Chen, Xiaofeng; Yang, Yunxu; Xiao, Min; Li, Yongfang

2017-10-01

Suppression of carrier recombination is critically important in realizing high-efficiency polymer solar cells. Herein, it is demonstrated difluoro-substitution of thiophene conjugated side chain on donor polymer can suppress triplet formation for reducing carrier recombination. A new medium bandgap 2D-conjugated D-A copolymer J91 is designed and synthesized with bi(alkyl-difluorothienyl)-benzodithiophene as donor unit and fluorobenzotriazole as acceptor unit, for taking the advantages of the synergistic fluorination on the backbone and thiophene side chain. J91 demonstrates enhanced absorption, low-lying highest occupied molecular orbital energy level, and higher hole mobility, in comparison with its control polymer J52 without fluorination on the thiophene side chains. The transient absorption spectra indicate that J91 can suppress the triplet formation in its blend film with n-type organic semiconductor acceptor m-ITIC (3,9-bis(2-methylene-(3-(1,1-dicyanomethylene)-indanone)-5,5,11,11-tetrakis(3-hexylphenyl)-dithieno[2,3-d:2,3'-d']-s-indaceno[1,2-b:5,6-b']-dithiophene). With these favorable properties, a higher power conversion efficiency of 11.63% with high V OC of 0.984 V and high J SC of 18.03 mA cm -2 is obtained for the polymer solar cells based on J91/m-ITIC with thermal annealing. The improved photovoltaic performance by thermal annealing is explained from the morphology change upon thermal annealing as revealed by photoinduced force microscopy. The results indicate that side chain engineering can provide a new solution to suppress carrier recombination toward high efficiency, thus deserves further attention. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Crystal structure of a looped-chain CoII coordination polymer: catena-poly[[bis-(nitrato-κO)cobalt(II)]bis-[μ-bis-(pyridin-3-ylmeth-yl)sulfane-κ2N:N'

PubMed

Moon, Suk-Hee; Seo, Joobeom; Park, Ki-Min

2017-11-01

The asymmetric unit of the title compound, [Co(NO 3 ) 2 (C 12 H 12 N 2 S) 2 ] n , contains a bis-(pyridin-3-ylmeth-yl)sulfane ( L ) ligand, an NO 3 - anion and half a Co II cation, which lies on an inversion centre. The Co II cation is six-coordinated, being bound to four pyridine N atoms from four symmetry-related L ligands. The remaining coordination sites are occupied by two O atoms from two symmetry-related nitrate anions in a monodentate manner. Thus, the Co II centre adopts a distorted octa-hedral geometry. Two symmetry-related L ligands are connected by two symmetry-related Co II cations, forming a 20-membered cyclic dimer, in which the Co II atoms are separated by 10.2922 (7) Å. The cyclic dimers are connected to each other by sharing Co II atoms, giving rise to the formation of an infinite looped chain propagating along the [101] direction. Inter-molecular C-H⋯π (H⋯ring centroid = 2.89 Å) inter-actions between one pair of corresponding L ligands and C-H⋯O hydrogen bonds between the L ligands and the nitrate anions occur in the looped chain. In the crystal, adjacent looped chains are connected by inter-molecular π-π stacking inter-actions [centroid-to-centroid distance = 3.8859 (14) Å] and C-H⋯π hydrogen bonds (H⋯ring centroid = 2.65 Å), leading to the formation of layers parallel to (101). These layers are further connected through C-H⋯O hydrogen bonds between the layers, resulting in the formation of a three-dimensional supra-molecular architecture.

Rouse mode analysis of chain relaxation in homopolymer melts

DOE PAGES

Kalathi, Jagannathan T.; Kumar, Sanat K.; Rubinstein, Michael; ...

2014-09-15

We use molecular dynamics simulations of the Kremer–Grest (KG) bead–spring model of polymer chains of length between 10 and 500, and a closely related analogue that allows for chain crossing, to clearly delineate the effects of entanglements on the length-scale-dependent chain relaxation in polymer melts. We analyze the resulting trajectories using the Rouse modes of the chains and find that entanglements strongly affect these modes. The relaxation rates of the chains show two limiting effective monomeric frictions, with the local modes experiencing much lower effective friction than the longer modes. The monomeric relaxation rates of longer modes vary approximately inverselymore » with chain length due to kinetic confinement effects. The time-dependent relaxation of Rouse modes has a stretched exponential character with a minimum of stretching exponent in the vicinity of the entanglement chain length. None of these trends are found in models that allow for chain crossing. As a result, these facts, in combination, argue for the confined motion of chains for time scales between the entanglement time and their ultimate free diffusion.« less

White Polymer Light-Emitting Diodes Based on Exciplex Electroluminescence from Polymer Blends and a Single Polymer.

PubMed

Liang, Junfei; Zhao, Sen; Jiang, Xiao-Fang; Guo, Ting; Yip, Hin-Lap; Ying, Lei; Huang, Fei; Yang, Wei; Cao, Yong

2016-03-09

In this Article, we designed and synthesized a series of polyfluorene derivatives, which consist of the electron-rich 4,4'-(9-alkyl-carbazole-3,6-diyl)bis(N,N-diphenylaniline) (TPA-Cz) in the side chain and the electron-deficient dibenzothiophene-5,5-dioxide (SO) unit in the main chain. The resulting copolymer PF-T25 that did not comprise the SO unit exhibited blue light-emission with the Commission Internationale de L'Eclairage coordinates of (0.16, 0.10). However, by physically blending PF-T25 with a blue light-emitting SO-based oligomer, a novel low-energy emission correlated to exciplex emerged due to the appropriate energy level alignment of TPA-Cz and the SO-based oligomers, which showed extended exciton lifetime as confirmed by time-resolved photoluminescent spectroscopy. The low-energy emission was also identified in copolymers consisting of SO unit in the main chain, which can effectively compensate for the high-energy emission to produce binary white light-emission. Polymer light-emitting diodes based on the exciplex-type single greenish-white polymer exhibit the peak luminous efficiency of 2.34 cd A(-1) and the maximum brightness of 12 410 cd m(-2), with Commission Internationale de L'Eclairage color coordinates (0.27, 0.39). The device based on such polymer showed much better electroluminescent stability than those based on blending films. These observations indicated that developing a single polymer with the generated exciplex emission can be a novel and effective molecular design strategy toward highly stable and efficient white polymer light-emitting diodes.

Solvent induced synthesis, structure and properties of coordination polymers based on 5-hydroxyisophthalic acid as linker and 1,10-phenanthroline as auxiliary ligand

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kariem, Mukaddus; Yawer, Mohd; Sheikh, Haq Nawaz, E-mail: hnsheikh@rediffmail.com

2015-11-15

Three new coordination polymers [Mn(hip)(phen) (H{sub 2}O)]{sub n} (1), [Co(hip)(phen) (H{sub 2}O)]{sub n} (2), and [Cd(hip) (phen) (H{sub 2}O)]{sub n} (3) (H{sub 2}hip=5-hydroxyisophthalic acid; phen=1,10-phenanthroline) have been synthesized by solvo-hydrothermal method using diethyl formamide-water (DEF-H{sub 2}O) as solvent system. Single-crystal X-ray diffraction analysis reveals that all three coordination polymers 1, 2 and 3 crystallize in monoclinic space group P2/n. Metal ions are inter-connected by hydroxyisophthalate anions forming zig-zag 1D chain. 1D chains are further inter-connected by hydrogen bonding and π–π stacking interactions leading to 3D supramolecular architecture. Hydrogen-bonding and π–π stacking provide thermal stability to polymers. Compounds 1 and 2more » are paramagnetic at room temperature and variable temperature magnetic moment measurements revealed weak ferromagnetic interactions between metal ions at low temperature. Compound 3 exhibits excellent photoluminescence with large Stokes shift. - Graphical abstract: 1D helical chains of coordination polymers were synthesized by solvo-hydrothermal reaction of 5-hydroxyisopthalic acid and 1,10-phenanthroline with MnCl{sub 2}·4H{sub 2}O / CoCl{sub 2}·6H{sub 2}O / Cd(NO{sub 3}){sub 2}·6H{sub 2}O. - Highlights: • Solvent induced synthesis of three coordination polymers with 1D zig-zag structure. • Crystal structures of coordination polymers are reported and discussed. • 1,10-Phenanthroline influences magnetic and luminescent properties of polymers. • Coordination polymer of Cd is luminescent exhibiting large Stokes shift.« less

Pathways for degradation of plastic polymers floating in the marine environment.

PubMed

Gewert, Berit; Plassmann, Merle M; MacLeod, Matthew

2015-09-01

Each year vast amounts of plastic are produced worldwide. When released to the environment, plastics accumulate, and plastic debris in the world's oceans is of particular environmental concern. More than 60% of all floating debris in the oceans is plastic and amounts are increasing each year. Plastic polymers in the marine environment are exposed to sunlight, oxidants and physical stress, and over time they weather and degrade. The degradation processes and products must be understood to detect and evaluate potential environmental hazards. Some attention has been drawn to additives and persistent organic pollutants that sorb to the plastic surface, but so far the chemicals generated by degradation of the plastic polymers themselves have not been well studied from an environmental perspective. In this paper we review available information about the degradation pathways and chemicals that are formed by degradation of the six plastic types that are most widely used in Europe. We extrapolate that information to likely pathways and possible degradation products under environmental conditions found on the oceans' surface. The potential degradation pathways and products depend on the polymer type. UV-radiation and oxygen are the most important factors that initiate degradation of polymers with a carbon-carbon backbone, leading to chain scission. Smaller polymer fragments formed by chain scission are more susceptible to biodegradation and therefore abiotic degradation is expected to precede biodegradation. When heteroatoms are present in the main chain of a polymer, degradation proceeds by photo-oxidation, hydrolysis, and biodegradation. Degradation of plastic polymers can lead to low molecular weight polymer fragments, like monomers and oligomers, and formation of new end groups, especially carboxylic acids.

Path-Integration Computation of the Transport Properties of Polymers Nanoparticles and Complex Biological Structures

NASA Astrophysics Data System (ADS)

Douglas, Jack

2014-03-01

One of the things that puzzled me when I was a PhD student working under Karl Freed was the curious unity between the theoretical descriptions of excluded volume interactions in polymers, the hydrodynamic properties of polymers in solution, and the critical properties of fluid mixtures, gases and diverse other materials (magnets, superfluids,etc.) when these problems were formally expressed in terms of Wiener path integration and the interactions treated through a combination of epsilon expansion and renormalization group (RG) theory. It seemed that only the interaction labels changed from one problem to the other. What do these problems have in common? Essential clues to these interrelations became apparent when Karl Freed, myself and Shi-Qing Wang together began to study polymers interacting with hyper-surfaces of continuously variable dimension where the Feynman perturbation expansions could be performed through infinite order so that we could really understand what the RG theory was doing. It is evidently simply a particular method for resuming perturbation theory, and former ambiguities no longer existed. An integral equation extension of this type of exact calculation to ``surfaces'' of arbitrary fixed shape finally revealed the central mathematical object that links these diverse physical models- the capacity of polymer chains, whose value vanishes at the critical dimension of 4 and whose magnitude is linked to the friction coefficient of polymer chains, the virial coefficient of polymers and the 4-point function of the phi-4 field theory,...Once this central object was recognized, it then became possible solve diverse problems in material science through the calculation of capacity, and related ``virials'' properties, through Monte Carlo sampling of random walk paths. The essential ideas of this computational method are discussed and some applications given to non-trivial problems: nanotubes treated as either rigid rods or ensembles worm-like chains having finite cross-section, DNA, nanoparticles with grafted chain layers and knotted polymers. The path-integration method, which grew up from research in Karl Freed's group, is evidently a powerful tool for computing basic transport properties of complex-shaped objects and should find increasing application in polymer science, nanotechnological applications and biology.

Role of non-equilibrium conformations on driven polymer translocation

NASA Astrophysics Data System (ADS)

Katkar, H. H.; Muthukumar, M.

2018-01-01

One of the major theoretical methods in understanding polymer translocation through a nanopore is the Fokker-Planck formalism based on the assumption of quasi-equilibrium of polymer conformations. The criterion for applicability of the quasi-equilibrium approximation for polymer translocation is that the average translocation time per Kuhn segment, ⟨τ⟩/NK, is longer than the relaxation time τ0 of the polymer. Toward an understanding of conditions that would satisfy this criterion, we have performed coarse-grained three dimensional Langevin dynamics and multi-particle collision dynamics simulations. We have studied the role of initial conformations of a polyelectrolyte chain (which were artificially generated with a flow field) on the kinetics of its translocation across a nanopore under the action of an externally applied transmembrane voltage V (in the absence of the initial flow field). Stretched (out-of-equilibrium) polyelectrolyte chain conformations are deliberately and systematically generated and used as initial conformations in translocation simulations. Independent simulations are performed to study the relaxation behavior of these stretched chains, and a comparison is made between the relaxation time scale and the mean translocation time (⟨τ⟩). For such artificially stretched initial states, ⟨τ⟩/NK < τ0, demonstrating the inapplicability of the quasi-equilibrium approximation. Nevertheless, we observe a scaling of ⟨τ⟩ ˜ 1/V over the entire range of chain stretching studied, in agreement with the predictions of the Fokker-Planck model. On the other hand, for realistic situations where the initial artificially imposed flow field is absent, a comparison of experimental data reported in the literature with the theory of polyelectrolyte dynamics reveals that the Zimm relaxation time (τZimm) is shorter than the mean translocation time for several polymers including single stranded DNA (ssDNA), double stranded DNA (dsDNA), and synthetic polymers. Even when these data are rescaled assuming a constant effective velocity of translocation, it is found that for flexible (ssDNA and synthetic) polymers with NK Kuhn segments, the condition ⟨τ⟩/NK < τZimm is satisfied. We predict that for flexible polymers such as ssDNA, a crossover from quasi-equilibrium to non-equilibrium behavior would occur at NK ˜ O(1000).

Dynamic Self-Consistent Field Theories for Polymer Blends and Block Copolymers

NASA Astrophysics Data System (ADS)

Kawakatsu, Toshihiro

Understanding the behavior of the phase separated domain structures and rheological properties of multi-component polymeric systems require detailed information on the dynamics of domains and that of conformations of constituent polymer chains. Self-consistent field (SCF) theory is a useful tool to treat such a problem because the conformation entropy of polymer chains in inhomogeneous systems can be evaluated quantitatively using this theory. However, when we turn our attention to the dynamic properties in a non-equilibrium state, the basic assumption of the SCF theory, i.e. the assumption of equilibrium chain conformation, breaks down. In order to avoid such a difficulty, dynamic SCF theories were developed. In this chapter, we give a brief review of the recent developments of dynamic SCF theories, and discuss where the cutting-edge of this theory is.

Structure and phase behavior of a confined nanodroplet composed of the flexible chain molecules.

PubMed

Kim, Soon-Chul; Kim, Eun-Young; Seong, Baek-Seok

2011-04-28

A polymer density functional theory has been employed for investigating the structure and phase behaviors of the chain polymer, which is modelled as the tangentially connected sphere chain with an attractive interaction, inside the nanosized pores. The excess free energy of the chain polymer has been approximated as the modified fundamental measure-theory for the hard spheres, the Wertheim's first-order perturbation for the chain connectivity, and the mean-field approximation for the van der Waals contribution. For the value of the chemical potential corresponding to a stable liquid phase in the bulk system and a metastable vapor phase, the flexible chain molecules undergo the liquid-vapor transition as the pore size is reduced; the vapor is the stable phase at small volume, whereas the liquid is the stable phase at large volume. The wide liquid-vapor coexistence curve, which explains the wide range of metastable liquid-vapor states, is observed at low temperature. The increase of temperature and decrease of pore size result in a narrowing of liquid-vapor coexistence curves. The increase of chain length leads to a shift of the liquid-vapor coexistence curve towards lower values of chemical potential. The coexistence curves for the confined phase diagram are contained within the corresponding bulk liquid-vapor coexistence curve. The equilibrium capillary phase transition occurs at a higher chemical potential than in the bulk phase.

Linear rheology and structure of molecular bottlebrushes with short side chains

DOE Office of Scientific and Technical Information (OSTI.GOV)

López-Barrón, Carlos R., E-mail: carlos.r.lopez-barron@exxonmobil.com; Brant, Patrick; Crowther, Donna J.

We investigate the microstructure and linear viscoelasticity of model molecular bottlebrushes (BBs) using rheological and small-angle X-ray and neutron scattering measurements. Our polymers have short atactic polypropylene (aPP) side chains of molecular weight ranging from 119 g/mol to 259 g/mol and narrow molecular weight distribution (M{sub w}/M{sub n} 1.02–1.05). The side chain molecular weights are a small fraction of the entanglement molecular weight of the corresponding linear polymer (M{sub e,aPP}= 7.05 kg/mol), and as such, they are unentangled. The morphology of the aPP BBs is characterized as semiflexible thick chains with small side chain interdigitation. Their dynamic master curves, obtained by time-temperature superposition,more » reveal two sequential relaxation processes corresponding to the segmental relaxation and the relaxation of the BB backbone. Due to the short length of the side chains, their fast relaxation could not be distinguished from the glassy relaxation. The fractional free volume is an increasing function of the side chain length (N{sub SC}). Therefore, the glassy behavior of these polymers as well as their molecular friction and dynamic properties are influenced by their N{sub SC} values. The apparent flow activation energies are a decreasing function of N{sub SC}, and their values explain the differences in zero-shear viscosity measured at different temperatures.« less

Structural and optical properties of self-assembled chains of plasmonic nanocubes

DOE PAGES

Klinkova, Anna; Gang, Oleg; Therien-Aubin, Heloise; ...

2014-10-10

Solution-based linear self-assembly of metal nanoparticles offers a powerful strategy for creating plasmonic polymers, which, so far, have been formed from spherical nanoparticles and nanorods. Here, we report linear solution-based self-assembly of metal nanocubes (NCs), examine the structural characteristics of the NC chains and demonstrate their advanced optical characteristics. Predominant face-to-face assembly of large NCs coated with short polymer ligands led to a larger volume of hot spots in the chains, a nearly uniform E-field enhancement in the gaps between co-linear NCs and a new coupling mode for NC chains, in comparison with chains of nanospheres with similar dimensions, compositionmore » and surface chemistry. The NC chains exhibited a stronger surface enhanced Raman scattering (SERS) signal, in comparison with linear assemblies of nanospheres. The experimental results were in agreement with finite difference time domain (FDTD) simulations.« less

Local Structure and Ion Transport in Glassy Poly(ethylene oxide styrene) Copolymers

NASA Astrophysics Data System (ADS)

Yang, Han-Chang; Mays, Jimmy; Sokolov, Alexei P.; Winey, Karen I.

2014-03-01

Polymer electrolytes have attracted attention for a wide variety of applications in energy production such as lithium-ion batteries and fuel cells. The concept of free volume provides important information about ion mobility and chain dynamics in the polymer matrix. Researchers have recently demonstrated that ion transport in glassy polymer can be improved by designing a system with high free volume. We have studied the effect of temperature and humidity on the intermolecular correlations of poly(ethylene oxide styrene-block-styrene) (PEOSt- b-St) block copolymer and poly(ethylene oxide styrene) (PEOSt) homopolymer using in situ multi-angle x-ray scattering across a wide range of scattering angles (q = 0.007-1.5 Å-1) . An increase in backbone-to-backbone distance is observed, indicating an increase in free volume between different polymer main chains. Structural characterization of the polymer segments will be discussed together with conductivity and dielectric results to better understand the ion transport mechanism in the local environment of the polymer system. Department of Chemistry, University of Tennessee.

Effects of supercritical carbon dioxide on immobile bound polymer chains on solid substrates

NASA Astrophysics Data System (ADS)

Sen, Mani; Asada, Mitsunori; Jiang, Naisheng; Endoh, Maya K.; Akgun, Bulent; Satija, Sushil; Koga, Tadanori

2013-03-01

Adsorbed polymer layers formed on flat solid substrates have recently been the subject of extensive studies because it is postulated to control the dynamics of technologically relevant polymer thin films, for example, in lithography. Such adsorbed layers have been reported to hinder the mobility of polymer chains in thin films even at a large length scale. Consequently, this bound layer remains immobile regardless of processing techniques (i.e. thermal annealing, solvent dissolution, etc). Here, we investigate the use of supercritical carbon dioxide (scCO2) as a novel plasticizer for bound polystyrene layers formed on silicon substrates. In-situ swelling and interdiffusion experiments using neutron reflectivity were performed. As a result, we found the anomalous plasticization effects of scCO2 on the bound polymer layers near the critical point where the anomalous adsorption of CO2 molecules in polymer thin films has been reported previously. Acknowledgement: We acknowledge the financial support from NSF Grant No. CMMI-084626.

Molecular self assembly of mixed comb-like dextran surfactant polymers for SPR virus detection.

PubMed

Mai-Ngam, Katanchalee; Kiatpathomchai, Wansika; Arunrut, Narong; Sansatsadeekul, Jitlada

2014-11-04

The synthesis of two comb-like dextran surfactant polymers, that are different in their dextran molecular weight (MW) distribution and the presence of carboxylic groups, and their characterization are reported. A bimodal carboxylic dextran surfactant polymer consists of poly(vinyl amine) (PVAm) backbone with carboxyl higher MW dextran, non-functionalized lower MW dextran and hydrophobic hexyl branches; while a monomodal dextran surfactant polymer is PVAm grafted with non-functionalized lower MW dextran and hexyl branches. Layer formation of non-covalently attached dextran chains with bimodal MW distributions on a surface plasmon resonance (SPR) chip was investigated from the perspective of mixed physisorption of the bimodal and monomodal surfactant polymers. Separation distances between the carboxylic longer dextran side chains within the bimodal surfactant polymer and between the whole bimodal surfactant molecules on the chip surface could be well-controlled. SPR analysis of shrimp yellow head virus using our mixed surfactant chips showed dependence on synergetic adjustment of these separation distances. Copyright © 2014 Elsevier Ltd. All rights reserved.

Conformation and dynamics of polymer chains on dirty surfaces: A discrete-to-continuum approach

NASA Astrophysics Data System (ADS)

Foo, Grace M.; Pandey, R. B.

1998-07-01

A discrete-to-continuum (DC) simulation approach is introduced to study the statics and dynamics of polymer chains in two dimensions with quenched barriers, a dirty surface. In our DC hybrid approach, the large-scale relaxation of polymer chains on a discrete disordered lattice is followed by off-lattice simulation using a bead-spring chain model with a finitely extensible nonlinear elastic (FENE) potential for covalent bonds and Lennard-Jones (LJ) potential for nonbonded interactions. Segregation/folding of chains, which occurs at low temperatures (T=0.2, 1.0) with LJ interaction, becomes more difficult as the concentration of barriers increases, due to a screening effect of the barriers. In contrast to the chains' contraction at high temperature (i.e., T=5) and their collapse in athermal systems, chains are elongated on increasing the barrier concentration—a barrier-induced stretching. Variations of the root-mean-square (rms) displacements of the center of mass (Rcm) of the chains and their center node (Rcn) with time (t) show power-law behaviors (Rcm˜tν1, Rcn˜tν2) with nonuniversal exponents in the range ν1≃0.40-0.05 and ν2≃0.30-0.05, respectively, depending on temperature and barrier concentration. The radius of gyration (Rg) and the average bond length () expand on increasing the barrier concentration at low temperature and contract at high temperature, which is consistent with the variation of the width of the radial distribution function.

Novel Strategy for Photopatterning Emissive Polymer Brushes for Organic Light Emitting Diode Applications

PubMed Central

2017-01-01

A light-mediated methodology to grow patterned, emissive polymer brushes with micron feature resolution is reported and applied to organic light emitting diode (OLED) displays. Light is used for both initiator functionalization of indium tin oxide and subsequent atom transfer radical polymerization of methacrylate-based fluorescent and phosphorescent iridium monomers. The iridium centers play key roles in photocatalyzing and mediating polymer growth while also emitting light in the final OLED structure. The scope of the presented procedure enables the synthesis of a library of polymers with emissive colors spanning the visible spectrum where the dopant incorporation, position of brush growth, and brush thickness are readily controlled. The chain-ends of the polymer brushes remain intact, affording subsequent chain extension and formation of well-defined diblock architectures. This high level of structure and function control allows for the facile preparation of random ternary copolymers and red–green–blue arrays to yield white emission. PMID:28691078

Novel Strategy for Photopatterning Emissive Polymer Brushes for Organic Light Emitting Diode Applications.

PubMed

Page, Zachariah A; Narupai, Benjaporn; Pester, Christian W; Bou Zerdan, Raghida; Sokolov, Anatoliy; Laitar, David S; Mukhopadhyay, Sukrit; Sprague, Scott; McGrath, Alaina J; Kramer, John W; Trefonas, Peter; Hawker, Craig J

2017-06-28

A light-mediated methodology to grow patterned, emissive polymer brushes with micron feature resolution is reported and applied to organic light emitting diode (OLED) displays. Light is used for both initiator functionalization of indium tin oxide and subsequent atom transfer radical polymerization of methacrylate-based fluorescent and phosphorescent iridium monomers. The iridium centers play key roles in photocatalyzing and mediating polymer growth while also emitting light in the final OLED structure. The scope of the presented procedure enables the synthesis of a library of polymers with emissive colors spanning the visible spectrum where the dopant incorporation, position of brush growth, and brush thickness are readily controlled. The chain-ends of the polymer brushes remain intact, affording subsequent chain extension and formation of well-defined diblock architectures. This high level of structure and function control allows for the facile preparation of random ternary copolymers and red-green-blue arrays to yield white emission.

Megasupramolecules for safer, cleaner fuel by end association of long telechelic polymers

NASA Astrophysics Data System (ADS)

Wei, Ming-Hsin; Li, Boyu; David, R. L. Ameri; Jones, Simon C.; Sarohia, Virendra; Schmitigal, Joel A.; Kornfield, Julia A.

2015-10-01

We used statistical mechanics to design polymers that defy conventional wisdom by self-assembling into “megasupramolecules” (≥5000 kg/mol) at low concentration (≤0.3 weight percent). Theoretical treatment of the distribution of individual subunits—end-functional polymers—among cyclic and linear supramolecules (ring-chain equilibrium) predicts that megasupramolecules can form at low total polymer concentration if, and only if, the backbones are long (>400 kg/mol) and end-association strength is optimal. Viscometry and scattering measurements of long telechelic polymers having polycyclooctadiene backbones and acid or amine end groups verify the formation of megasupramolecules. They control misting and reduce drag in the same manner as ultralong covalent polymers. With individual building blocks short enough to avoid hydrodynamic chain scission (weight-average molecular weights of 400 to 1000 kg/mol) and reversible linkages that protect covalent bonds, these megasupramolecules overcome the obstacles of shear degradation and engine incompatibility.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wingert, Matthew C.; Jiang, Zhang; Chen, Renkun

Here, electrospun polymer nanofibers have garnered significant interest due to their strong size-dependent material properties, such as tensile moduli, strength, toughness, and glass transition temperatures. These properties are closely correlated with polymer chain dynamics. In most applications, polymers usually exhibit viscoelastic behaviors such as stress relaxation and creep, which are also determined by the motion of polymer chains. However, the size-dependent viscoelasticity has not been studied previously in polymer nanofibers. Here, we report the first experimental evidence of significant size-dependent stress relaxation in electrospun Nylon-11 nanofibers as well as size-dependent viscosity of the confined amorphous regions. In conjunction with themore » dramatically increasing stiffness of nano-scaled fibers, this strong relaxation enables size-tunable properties which break the traditional damping-stiffness tradeoff, qualifying electrospun nanofibers as a promising set of size-tunable materials with an unusual and highly desirable combination of simultaneously high stiffness and large mechanical energy dissipation.« less

Synthesis of interlocked molecules by olefin metathesis

NASA Astrophysics Data System (ADS)

Clark, Paul Gregory

A large body of work in the Grubbs group has focused on the development of functional-group tolerant ruthenium alkylidene catalysts that perform a number of olefin metathesis reactions. These catalysts have seen application in a wide range of fields, including classic total synthesis as well as polymer and materials chemistry. One particular family of compounds, interlocked molecules, has benefitted greatly from these advances in catalyst stability and activity. This thesis describes several elusive and challenging interlocked architectures whose syntheses have been realized through the utilization of different types of ruthenium-catalyzed olefin metathesis reactions. Ring-closing olefin metathesis has enabled the synthesis of a [c2]daisy-chain dimer with the ammonium binding site near the cap of the dimer. A deprotonated DCD possessing such a structural attribute will more forcefully seek to restore coordinating interactions upon reprotonation, enhancing its utility as a synthetic molecular actuator. Dimer functionalization facilitated incorporation into linear polymers, with a 48% size increase of an unbound, extended analogue of the polymer demonstrating slippage of the dimer units. Ongoing work is directed at further materials studies, in particular, exploring the synthesis of macroscopic networks containing the DCD units and analyzing the correlation between molecular-scale extension-contraction manipulations and resulting macro-scale changes. A "clipping" approach to a polycatenated cyclic polymer, a structure that resembles a molecular "charm bracelet", has been described. The use of ring-opening metathesis polymerization of a carbamate monomer in the presence of a chain transfer agent allowed for the synthesis of a linear polymer that was subsequently functionalized and cyclized to the corresponding cyclic analogue. This cyclic polymer was characterized through a variety of techniques, and subjected to further functionalization reactions, affording a cyclic polyammonium scaffold. Diolefin polyether fragments were coordinated and "clipped" around the ammonium sites within the polymer backbone using ring-closing olefin metathesis, giving the molecular "charm bracelet". Confirmation of the interlocked nature of the product was achieved via 1H NMR spectroscopy and two-dimensional diffusion ordered NMR spectroscopy. A simple strategy for a one-pot, multi-component synthesis of polyrotaxanes using acyclic diene metathesis polymerization was developed. The polyrotaxanes were characterized by traditional 1H NMR spectroscopy as well as size exclusion chromatography, and the interlocked topology was confirmed using two-dimension diffusion-ordered NMR spectroscopy. The dynamic, self-correcting nature of the ADMET polymerization was also explored through the equilibration of a capped polyammonium polymer in the presence of dibenzo-24-crown-8 ether and olefin metathesis catalysts. The efficiency and ease with which these mechanically interlocked macromolecules can be assembled should facilitate rapid modulation to achieve versatile polyrotaxane architectures. Flexible, switchable [c2]daisy-chain dimers (DCDs) were synthesized, where the macromer ammonium binding site was adjacent to the crown-type recognition structure and separated from the cap by an alkyl chain. A DCD of this topology is expected to have an extended structure in the bound conformation (when the ammonium was coordinated to the crown). Several different macromer candidates were designed to allow access to DCDs with flexible alkyl chains between the ammonium binding site and the cap, and a number of synthetic routes were explored in an effort to access these challenging materials. While the first generation DCD structure proved to be unstable due to a labile ester linkage, work is continuing toward the development of several cap structures in an effort to replace the ester linkage with an ether linkage, which, in the second generation model systems, has proven much more stable to the acidic and basic conditions necessary to induce switching of the dimeric architecture. One of the efforts in our lab is directed at the synthesis of 18F-labeled nanoparticles to be used as tumor imaging agents in positron emission tomography. We have been working to optimize fluorine incorporation while minimizing NP crosslinking. Because of evidence of NP side-reactions with the potassium carbonate base, we have begun to use potassium benzoate solid-state beads. To analyze the fluorinated NPs, various sorbents were explored. It was found that silica sorbents rapidly reacted and bound to the NPs, while the NPs remained unreactive and mobile on alumina. Further analysis of the NPs has been accomplished using 2D-DOSY NMR spectroscopy. Future work with the NPs will involve a systematic evaluation of the role of water on the extent of fluorination, as well as functionalization of the NPs with Cy5.5 dye for use in studies on eyes to be done in collaboration with researchers at the Mayo Clinic.

Synthesis of High Molecular Weight Poly(glycerol monomethacrylate) via RAFT Emulsion Polymerization of Isopropylideneglycerol Methacrylate

PubMed Central

2018-01-01

High molecular weight water-soluble polymers are widely used as flocculants or thickeners. However, synthesis of such polymers via solution polymerization invariably results in highly viscous fluids, which makes subsequent processing somewhat problematic. Alternatively, such polymers can be prepared as colloidal dispersions; in principle, this is advantageous because the particulate nature of the polymer chains ensures a much lower fluid viscosity. Herein we exemplify the latter approach by reporting the convenient one-pot synthesis of high molecular weight poly(glycerol monomethacrylate) (PGMA) via the reversible addition–fragmentation chain transfer (RAFT) aqueous emulsion polymerization of a water-immiscible protected monomer precursor, isopropylideneglycerol methacrylate (IPGMA) at 70 °C, using a water-soluble poly(glycerol monomethacrylate) (PGMA) chain transfer agent as a steric stabilizer. This formulation produces a low-viscosity aqueous dispersion of PGMA–PIPGMA diblock copolymer nanoparticles at 20% solids. Subsequent acid deprotection of the hydrophobic core-forming PIPGMA block leads to particle dissolution and affords a viscous aqueous solution comprising high molecular weight PGMA homopolymer chains with a relatively narrow molecular weight distribution. Moreover, it is shown that this latex precursor route offers an important advantage compared to the RAFT aqueous solution polymerization of glycerol monomethacrylate since it provides a significantly faster rate of polymerization (and hence higher monomer conversion) under comparable conditions. PMID:29805184