Supramolecular materials for inkjet printing: self-assembling polymer networks

Electronically complementary, low molecular weight polymers that self-assemble through tuneable π-π stacking interactions to form extended supramolecular polymer networks have been developed for inkjet printing applications and successfully deposited using three different printing techniques. Sequential overprinting of the complementary components results in supramolecular network formation through complexation of π-electron rich pyrenyl or perylenyl chain-ends in one component with π-electron deficient naphthalene diimide residues in a chain-folding polyimide. The complementary π-π stacked polymer blends generate strongly coloured materials as a result of charge-transfer absorptions in the visible spectrum, potentially negating the need for pigments or dyes in the ink formulation. Indeed, the final colour of the deposited material can be tailored by changing varying the end-groups of the π electron rich polymer component. Piezoelectric printing techniques were employed in a proof of concept study to allow characterisation of the materials deposited, and a thermal inkjet printer adapted with imaging software enabled a detailed analysis of the ink-drops as they formed, and of their physical properties. Finally, continuous inkjet printing allowed greater volumes of material to be deposited, on a variety of different substrate surfaces, and demonstrated the utility and versatility of this novel type of ink for industrial applications.

Perylene as an electron-rich moiety in healable, complementary π–π stacked, supramolecular polymer systems

A two-component, supramolecular polymer blend has been designed using a novel π-electron rich bisperylene- terminated polyether. This polymer is able to self-assemble through electronically complementary π–π stacking interactions with a π-electron-deficient chain-folding polydiimide to afford thermally healable polymer blends. Model compounds were developed to assess the suitability of the deep green complexes formed between perylene residues and chain-folding bis-diimides for use in polymer blends. The polymer blends thus synthesised were elastomeric in nature and demonstrated healable properties as demonstrated by scanning electron microscopy. Healing was observed to occur rapidly at ca. 75 degC, and excellent healing efficiencies were found by tensometric and rheometric analyses. These tuneable, stimuli-responsive, supramolecular polymer blends are compared to related healable blends featuring pyrene-terminated oligomers.

Microphase separation induced in the melt of Pluronic copolymers by blending with a hydrogen bonding urea–urethane end-capped supramolecular polymer

Blending with a hydrogen-bonding supramolecular polymer is shown to be a successful novel strategy to induce microphase-separation in the melt of a Pluronic polyether block copolymer. The supramolecular polymer is a polybutadiene derivative with urea–urethane end caps. Microphase separation is analysed using small-angle X-ray scattering and its influence on the macroscopic rheological properties is analysed. FTIR spectroscopy provides a detailed picture of the inter-molecular interactions between the polymer chains that induces conformational changes leading to microphase separation.

Synthesis, characterisation and magnetic properties of a one-dimensional Iron(II) coordination polymer

A new iron(II) coordination polymer, [FeCl2(NC7H9)2(N2C12H12)], has been synthesized under solvothermal conditions and structurally characterized by single-crystal X-ray diffraction. This material crystallizes in the monoclinic space group C2/c, with a = 11.2850(6), b = 13.8925(7), c = 17.0988(9) Å and β = 94.300(3)º (Z = 4). The crystal structure consists of neutral zig-zag chains, in which the iron(II) ions are octahedrally coordinated. The infinite polymer chains are packed into a three-dimensional structure through C–H···Cl interactions. Magnetic susceptibility measurements reveal the existence of weak antiferromagnetic interactions between the iron(II) ions. The effective magnetic moment, μ eff = 5.33 μ B , is consistent with a high-spin iron(II) configuration.

Donor-acceptor π−π stacking interactions: from small molecule complexes to healable supramolecular polymer networks

This chapter presents selected literature examples to review the development of the use of donor–acceptor π–π stacking interactions as transient cross-links in supramolecular polymer networks. The chapter examines notable examples of these highly specific and directional interactions and illustrates how they can be utilised to reliably produce functional supramolecular, self-assembled systems. Knowledge gained from these fundamental studies has enabled the design, synthesis and application of donor–acceptor stacked supramolecular motifs in non-covalent polymer networks, which is exemplified through detailing the production, physical properties and optimisation of healable materials.

CLEC-2 expression is maintained on activated platelets and on platelet microparticles

The C-type lectin-like receptor CLEC-2 mediates platelet activation through a hem-immunoreceptor tyrosine-based activation motif (hemITAM). CLEC-2 initiates a Src- and Syk-dependent signaling cascade that is closely related to that of the 2 platelet ITAM receptors: glycoprotein (GP)VI and FcγRIIa. Activation of either of the ITAM receptors induces shedding of GPVI and proteolysis of the ITAM domain in FcγRIIa. In the present study, we generated monoclonal antibodies against human CLEC-2 and used these to measure CLEC-2 expression on resting and stimulated platelets and on other hematopoietic cells. We show that CLEC-2 is restricted to platelets with an average copy number of ∼2000 per cell and that activation of CLEC-2 induces proteolytic cleavage of GPVI and FcγRIIa but not of itself. We further show that CLEC-2 and GPVI are expressed on CD41+ microparticles in megakaryocyte cultures and in platelet-rich plasma, which are predominantly derived from megakaryocytes in healthy donors, whereas microparticles derived from activated platelets only express CLEC-2. Patients with rheumatoid arthritis, an inflammatory disease associated with increased microparticle production, had raised plasma levels of microparticles that expressed CLEC-2 but not GPVI. Thus, CLEC-2, unlike platelet ITAM receptors, is not regulated by proteolysis and can be used to monitor platelet-derived microparticles.

Morphology of polymer networks formed in the chiral and non chiral phases of an anti-ferroelectric liquid crystal

We introduced photo-polymer networks into the various liquid crystalline phases of the antiferroelectric liquid crystal AS612 and studied the effects of these networks by measuring the temperature dependence of the Bragg wavelengths selectively reflected. After polymerization, the decrease in Bragg wavelengths with respect to the original values is consistent with a shorter helical pitch due to polymer network shrinkage. Also, by removing the liquid crystalline material, we are able to image the residual polymer network using scanning electron microscopy and polarized light microscopy. The polymer strands are a few microns thick and the networks show both chiral and non-chiral features.

Simulating startup shear of entangled polymer melts

Start-up shear rheology is a standard experiment used for characterizing polymer flow, and to test various models of polymer dynamics. A rich phenomenology is developed for behavior of entangled monodisperse linear polymers in such tests, documenting shear stress overshoots as a function of shear rates and molecular weights. A tube theory does a reasonable qualitative job at describing these phenomena, although it involves several drastic approximations and the agreement can be fortuitous. Recently, Lu and coworkers published several papers [e.g. Lu {\it et al.} {\it ACS Macro Lett}. 2014, 3, 569-573] reporting results from molecular dynamics simulations of linear entangled polymers, which contradict both theory and experiment. Based on these observations, they made very serious conclusions about the tube theory, which seem to be premature. In this letter, we repeat simulations of Lu {\it et al.} and systematically show that neither their simulation results, nor their comparison with theory are confirmed.

Large deviations of Rouse polymer chain: first passage problem

The purpose of this paper is to investigate several analytical methods of solving first passage (FP) problem for the Rouse model, a simplest model of a polymer chain. We show that this problem has to be treated as a multi-dimensional Kramers' problem, which presents rich and unexpected behavior. We first perform direct and forward-flux sampling (FFS) simulations, and measure the mean first-passage time $\tau(z)$ for the free end to reach a certain distance $z$ away from the origin. The results show that the mean FP time is getting faster if the Rouse chain is represented by more beads. Two scaling regimes of $\tau(z)$ are observed, with transition between them varying as a function of chain length. We use these simulations results to test two theoretical approaches. One is a well known asymptotic theory valid in the limit of zero temperature. We show that this limit corresponds to fully extended chain when each chain segment is stretched, which is not particularly realistic. A new theory based on the well known Freidlin-Wentzell theory is proposed, where dynamics is projected onto the minimal action path. The new theory predicts both scaling regimes correctly, but fails to get the correct numerical prefactor in the first regime. Combining our theory with the FFS simulations lead us to a simple analytical expression valid for all extensions and chain lengths. One of the applications of polymer FP problem occurs in the context of branched polymer rheology. In this paper, we consider the arm-retraction mechanism in the tube model, which maps exactly on the model we have solved. The results are compared to the Milner-McLeish theory without constraint release, which is found to overestimate FP time by a factor of 10 or more.

Exploiting thermally-reversible chemistry for controlling the crosslinking of polymer networks

High explosives are highly sensitive to accidental detonation by impact, fire, shrapnel and small arms fire. This sensitivity can be reduced by storing the energetic material within a rubbery polymer matrix and are known as plastic bonded explosives (PBX). The current procedure used to manufacture PBX involves mixing the energetic material with a hydroxy-functionalised aliphatic polymer. Upon the addition of an isocyanate crosslinker an immediate polymerisation occurs and thus the rapidly curing mixture must be used to fill the missile or shells, referred to as ‘stores’. This process can lead to poor distribution of the crosslinker resulting in the formation of an inhomogeneously crosslinked matrix and the formation of voids. One solution to this problem involves containing the crosslinker within polyurethane microcapsules that are uniformly dispersed in the explosive-polymer mixture. Upon the application of a stimulus the crosslinker can be released from the microcapsules and the formation of a uniformly crosslinked PBX achieved. Herein is reported the design and synthesis of polyurethane microcapsules that release isocyanate crosslinkers when desired using a thermal stimulus. This has been achieved by exploiting the thermally-reversible nature of oxime-urethane and Diels-Alder adducts that have been incorporated into the shell wall of the microcapsules. An alternative approach to controlling the polymerisation of PBX materials has also been achieved using thermally-reversible blocked isocyanates that regenerate the isocyanate crosslinker when exposed to heat.

Effective interaction between monolayers of block copolymer compatiblizer in a polymer blend

The stability of ternary blends of two immiscible homopolymers and a block copolymer compatiblizer depends crucially on the effective interaction between the copolymermonolayers that form between the unlike homopolymer domains. Here, the interaction is calculated for blends involving A and B homopolymers of equal size with ABABdiblock copolymers of symmetric composition using both self-consistent field theory (SCFT) and strong-segregation theory (SST). If the homopolymers are larger than the copolymer molecules, an attractive interaction is predicted which would destroy the blend. This conclusion coupled with considerations regarding the elastic properties of the monolayer suggests that the optimum size of the homopolymer molecules is about 80% that of the copolymer molecule. A detailed examination of the theory demonstrates that the attraction results from the configurational entropy loss of the homopolymer molecules trapped between the copolymermonolayers. We conclude by suggesting how the monolayers can be altered in order to suppress this attraction and thus improve compatiblization.

Application of abrupt cut-off models in the analysis of the capacitance spectra of conjugated polymer devices

In this paper, a detailed study of the capacitance spectra obtained from Au/doped-polyaniline/Al structures in the frequency domain (0.05 Hz-10 MHz), and at different temperatures (150-340 K) is carried out. The capacitance spectra behavior in semiconductors can be appropriately described by using abrupt cut-off models, since they assume that the electronic gap states that can follow the ac modulation have response times varying rapidly with a certain abscissa, which is dependent on both temperature and frequency. Two models based on the abrupt cut-off concept, formerly developed to describe inorganic semiconductor devices, have been used to analyze the capacitance spectra of devices based on doped polyaniline (PANI), which is a well-known polymeric semiconductor with innumerous potential technological applications. The application of these models allowed the determination of significant parameters, such as Debye length (approximate to 20 nm), position of bulk Fermi level (approximate to 320 meV) and associated density of states (approximate to 2x10(18) eV(-1) cm(-3)), width of the space charge region (approximate to 70 nm), built-in potential (approximate to 780 meV), and the gap states` distribution.

3D Cell-Migration Studies using Two-Photon Engineered Polymer Scaffolds

We use two-photon polymerization to fabricate 3D scaffolds with precise control over pore size and shape for studying cell migration in 3D. These scaffolds allow movement of cells in all directions. The fabrication, imaging, and quantitative analysis method developed here can be used to do systematic cell studies in 3D.

Magnetic resonance and conductivity study of gelatin-based proton conductor polymer electrolytes

This work report results from proton nuclear magnetic resonance (NMR), continuous-wave (CW-EPR) and pulsed electron paramagnetic resonance (P-EPR) and complex impedance spectroscopy of gelatin-based polymer gel electrolytes containing acetic acid. cross-linked with formaldehyde and plasticized with glycerol. Ionic conductivity of 2 x 10(-5) S/cm was obtained at room temperature for samples prepared with 33 wt% of acetic acid. Proton ((1)H) line shapes and spin-lattice relaxation times were measured as a function of temperature. The NMR results show that the proton mobility is dependent on acetic acid content in the plasticized polymer gel electrolytes. The CW-EPR spectra, which were carried out in samples doped with copper perchlorate, indicate the presence of the paramagnetic Cu(2+) ions in axially distorted sites. The P-EPR technique, known as electron spin echo envelope modulation (ESEEM), was employed to show the involvement of both, hydrogen and nitrogen atoms, in the copper complexation of the gel electrolyte. (C) 2009 Elsevier Ltd. All rights reserved.

Elastomeric Composites Based on Ethylene-Propylene-Diene Monomer Rubber and Conducting Polymer-Modified Carbon Black

Thermally stable elastomeric composites based on ethylene-propylene-diene monomer (EPDM) and conducting polymer-modified carbon black (CPMCB) additives were produced by casting and crosslinked by compression molding. CPMCB represent a novel thermally stable conductive compound made via ""in situ"" deposition of intrinsically conducting polymers (ICP) such as polyaniline or polypyrrole on carbon black particles. Thermogravimetric analysis showed that the composites are thermally stable with no appreciable degradation at ca. 300 degrees C. Incorporating CPMCB has been found to be advantageous to the processing of composites, as the presence of ICP lead to a better distribution of the filler within the rubber matrix, as confirmed by morphological analysis. These materials have a percolation threshold range of 5-10 phr depending on the formulation and electrical dc conductivity values in the range of 1 x 10(-3) to 1 x 10(-2) S cm(-1) above the percolation threshold. A less pronounced reinforcing effect was observed in composites produced with ICP-modified additives in relation to those produced only with carbon black. The results obtained in this study show the feasibility of this method for producing stable, electrically conducting composites with elastomeric characteristics. POLYM. COMPOS., 30:897-906, 2009. (C) 2008 Society of Plastics Engineers