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PubMed2006

Influence of aggregates and solvent aromaticity on the emission of conjugated polymers.

The influence of aggregates and solvent aromaticity on the photophysics and fluorescence dynamics of two conjugated polymers is studied. The two polymers are derivatives of poly(p-phenylene vinylene) (PPV) containing different kinked moieties along the main chain. The polymers contain 2,6-diphenylpyridine and m-terphenyl kinked moieties and they are abbreviated as PN and PC, respectively. The insertion of kinked segments along the main chain shifts the emission spectrum from the yellow-orange spectral region, common to PPV derivatives, to the blue-green spectral region. The results show that in dilute solutions the polymers decay monoexponentially, while in concentrated ones the fluorescence decays biexponentially, indicating fluorescence quenching. This is attributed to an energy transfer process from polymer chains to aggregates that occurs within a few tens of picoseconds. By comparing the photophysics and fluorescence dynamics of polymer PN in a nonaromatic and an aromatic solvent, we conclude that the polymer conformation adopted in the aromatic solvent leads to a higher fluorescence quantum yield and a longer fluorescence lifetime. Furthermore, the fluorescence quenching of PN because of aggregates is faster and more efficient in the aromatic than in the nonaromatic solvent. These results can be explained through a more extended chain conformation of PN in the aromatic solvent.

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PubMed2005

Use of linear polymers to control the preparation of luminescent organic microcrystals.

Microcrystals of an organic fluorescent dye, 4-octylamino-7-nitrobenz-2-oxa-1,3-diazole, were generated using the reprecipitation method, which is a solvent exchange process. In the presence of polymers, namely, poly(acrylic acid), molecular weight 5100 g mol(-1) and 15 000 g mol(-1), and poly(acrylic acid-co-maleic acid), average molecular weight about 50 000 g mol(-1), used as their sodium salts, the reprecipitation process was strongly accelerated. The reprecipitation kinetics was monitored by UV/vis absorption spectroscopy and revealed a three-step mechanism, each step being influenced by the polymer. The size and shape of the microcrystals were analyzed by fluorescence microscopy. The microcrystals obtained in the presence of polymers were smaller and more regular than those prepared in water alone and were not agglomerated. When the polymer was placed in the reprecipitation medium before introducing the dye solution, the microcrystals displayed a rectangular shape. When the polymer was introduced 20 min after the beginning of the reprecipitation process, intricately structured flowerlike microcrystals were observed. Microanalysis revealed that the microcrystals contained noticeable amounts of polymer. The measurement of the surface electric zeta potential suggested that a proportion of the polymer was present at the microcrystal surface. This work gives a thorough insight into a field where trials have until now been performed in an empirical way. It opens new perspectives to produce low-cost organic microcrystals, potentially useful in optics or pharmaceutical sciences.

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PubMed2005

Architectural and structural optimization of the protective polymer layer for enhanced targeting.

Using Monte Carlo simulations we study the influence of ligand architecture (valence, branching length) and structure (polydispersity) of a flat protective polymer layer on the accessibility of its functional groups and efficiency of receptor targeting. Two types of receptor surfaces were considered: the surface homogeneously covered with receptors and the surface containing a finite number of receptor sites. We found that multivalent ligands provide a larger density of targeting groups on the periphery of the layer compared to monovalent ligands for the same overall number of targeting groups per polymer layer. Because of their cooperativity in binding, multivalent ligands were also considerably more efficient in binding to both types of receptor surfaces. With an increase of ligand valence the number of functional groups attached to receptors noticeably increases. Short-branched divalent ligands show an especially high cooperativity in binding to closely packed receptors. However, in the case of immobile receptors separated by a finite distance from each other, the average distance between the functional groups belonging to the same short divalent ligand is too small to reach different receptors simultaneously and the receptor binding is less efficient than in the monovalent ligand case. Using a bidisperse protective polymer layer formed by short nonfunctional polymers and long functionalized polymers considerably increases the fraction of functional groups on the periphery of the layer. Simulations of receptor binding confirm the high efficiency of receptor targeting by bidisperse polymer layers, which is achieved by means of larger compressibility and higher capability of the ligands to reach out compared to the corresponding monodisperse layers. The concepts of multivalent ligands and a bidisperse protective polymer layer each have their own advantages which can be combined for an enhanced targeting effect.

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PubMed2004

Simple model for grafted polymer brushes.

The first theories of grafted polymer brushes assumed a step profile for the monomer density. Later, the real density profile was obtained from Monte Carlo or molecular dynamics simulations and calculated numerically using a self-consistent field theory. The analytical approximations of the solutions of the self-consistent field equations provided a parabolic dependence of the self-consistent field, which in turn led to a parabolic distribution for the monomer density in neutral brushes. As shown by numerical simulations, this model is not accurate for dense polymer brushes, with highly stretched polymers. In addition, the scaling laws obtained from the analytical approximations of the self-consistent field theory are identical to those derived from the earlier step-profile-approximation and predict a vanishing thickness of the brush at low graft densities, and a thickness exceeding the length of the polymer chains at high graft densities. Here a simple model is suggested to calculate the monomer density and the interaction between surfaces with grafted polymer brushes, based on an approximate calculation of the partition function of the polymer chains. The present model can be employed for both good and poor solvents, is compatible with a parabolic-like profile at moderate graft densities, and leads to an almost steplike density for highly stretched brushes. While the thickness of the brush depends strongly on solvent quality, it is a continuous function in the vicinity of the temperature. In good and moderately poor solvents, the interactions between surfaces with grafted polymer brushes are always repulsive, whereas in poor solvents the interactions are repulsive at small separations and become attractive at intermediate separation distances, in agreement with experiment. At large separations, a very weak repulsion is predicted.

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PubMed2005

Structure and dynamics of polymer-grafted clay suspensions.

The structure and dynamics of polymer-grafted two-dimensional silicate layers in solution were investigated. The geometry of the individual silicate layers was examined by looking at both polarized and depolarized light scattering from dilute solutions, while higher-concentration systems were used to study the interaction and dynamics of polymer-grafted silicate layers in suspension. The form factor for an oblate ellipsoid was used to fit the polarized intensity profile, and values of a approximately 80 nm and b approximately 380 nm for the semi-axes were obtained. The 80 nm value compares reasonably with the dimensions of the polymer brushes grafted on the surface of the silicate layers. The modulus of the grafted silicate in solution, as determined by Brillouin scattering, is of the order of 10 GPa. The cooperative diffusion mechanism, typical of interacting polymer chains, is suppressed due to the high polymer osmotic pressure. The osmotic pressure is also responsible for the weak interpenetration of the densely grafted polymer chains on the surface of the silicate layers. The scattering data indicates that the polymer-grafted nanoparticles move via collective diffusion and experience significant decrease in mobility above their overlap concentration.

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PubMed2006

Cross-linked and chemically functionalized polymer supports by reactive reversal nanoimprint lithography.

A new format of polymer support having cross-linked polymeric micro- and nanoarrays has been fabricated via reactive reversal nanoimprint lithography. Reactive reversal nanoimprint lithography is a relatively simple method to imprint highly cross-linked and chemically tunable polymers. An array of chloromethyl-functionalized cross-linked polystyrene has been imprinted on hard (silicon) and soft (polymer) substrates, and a model esterification reaction is demonstrated. The imprints have been found to be relatively stable under both static and dynamic stability tests carried out in various organic solvents. The chemical functionality is evenly distributed over the imprinted array. This method of fabricating polymer supports offers a high degree of freedom in terms of the choice of chemical functionality, the types of polymer matrix, and the size of the polymer support. The functional polymer support has potential applications for chemical and biological assays.

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PubMed2007

Stimuli-responsive polyelectrolyte polymer brushes prepared via atom-transfer radical polymerization.

We present an account of our research into polyelectrolyte polymer brushes that are capable of acting as stimuli-responsive films. We first detail the synthesis of poly(acrylic acid) polymer brushes using ATRP in a "grafting from" strategy. Significantly, we employed a chemical-free deprotection step that should leave the anchoring ester groups intact. We have demonstrated how these polymer assemblies respond to stimuli such as pH and electrolyte concentration. We have used poly(acrylic acid) polymer brushes for the synthesis of metallic nanoparticles and review this work. We have used XPS, ATR-FTIR, and AFM spectroscopy to show the presence of silver and palladium nanoparticles within polymer brushes. Finally, we report the synthesis of AB diblock polyampholyte polymer brushes that represent an extension of polyelectrolyte polymer brushes.

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PubMed1998

Dynamics of Polymer Interdiffusion: The Ripple Experiment.

We explore the interdiffusion of oppositely labeled triblock polystyrene chains, HDH/DHD, during welding in the melt using dynamic secondary ion mass spectroscopy (DSIMS) and specular neutron reflectivity (SNR). The HDH chains have the central portion of the chain deuterated (D) approximately 50% while the two ends (H) each have approximately 25% protonation; the DHD is oppositely labeled, but each set of chains contains about 50% deuteration. During welding, the deuterium depth profile exhibits "ripples" whose characteristic features, such as the time and molecular weight dependent shape, amplitude, and position, are very sensitive to the microscopic details of the polymer dynamics. The ripple experiment is especially sensitive to the presence, or absence, of topological constraints and anisotropic motion of chains. The current work significantly extends the molecular weight range up to 400 000. This allows greater separation of the six key ripple features used in deciphering the correct polymer dynamics model at the polymer-polymer interface. The DSIMS and SNR experimental results are compared to theoretical predictions and ripple simulations for Rouse, polymer mode-coupling, reptation (with and without tube broadening), and other phenomenological dynamics models. The six ripple characteristics were found to be perfectly correlated and convincingly consistent with the predictions of the reptation dynamics model. The ripple results are in significant disagreement with the polymer mode-coupling model proposed by Schweizer and other tubeless models. We conclude that the reptation model, proposed by DeGennes in 1971 with parallel developments by Edwards, is the correct model to describe the dynamics of polymer interdiffusion.

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PubMed1997

Characterization of anticholinesterase-active 3-alkylpyridinium polymers from the marine sponge Reniera sarai in aqueous solutions.

From the marine sponge Reniera sarai 3-alkylpyridinium oligomers and polymers have been isolated. 3-Alkylpyridinium polymers are potent anticholinesterase agents; in addition, they show hemolytic and cytotoxic activities. Oligomers with a molecular weight lower than 3000 Da do not possess any significant activity. We report structural characterization of 3-alkylpyridinium polymers and their behavior in aqueous solutions. We found that biologically active polymers are composed of head-to-tail 3-alkylpyridinium units. According to MALDI-TOF spectrometry two species of polymers exist, the smaller with a molecular weight of 5520 Da and the larger with a molecular weight of 18,900 Da. Both polymers are soluble only in water, while low molecular oligomers are readily soluble in organic solvents. Polymers form large water-dissolved supramolecular structures with an average hydrodynamic radius of 23 +/- 2 nm and, therefore, cannot be separated with size-exclusion chromatography.

Animals↗

PubMed2002

Polymer delivery of camptothecin against 9L gliosarcoma: release, distribution, and efficacy.

Camptothecin is a potent antineoplastic agent that has shown efficacy against multiple tumor lines in vitro; unfortunately, systemic toxicity has limited its in vivo efficacy. This is the first study to investigate the release, biodistribution, and efficacy of camptothecin from a biodegradable polyanhydride polymer. Tritiated camptothecin was incorporated into biodegradable polymers that were implanted intracranially in 16 male Fischer 344 rats and the animals were followed up to 21 days post-implant. A concentration of 11-45 microg of camptothecin-sodium/mg brain tissue was within a 3 mm radius of the polymer disc, with levels of 0.1 microg at the outermost margin of the rat brain, 7 mm from the site of implantation. These tissue concentrations are within the therapeutic ranges for human and rat glioma lines tested against camptothecin-sodium in vitro. The in vivo efficacy of camptothecin-sodium was evaluated with male Fischer 344 rats implanted intracranially with 9L gliosarcoma and compared with the efficacy of 1,3-bis(2-chloroethyl)-1-nitrosourea (BCNU). The animals were divided into four groups. Group 1 (control) had a median survival of 17 days. Group 2 (3.8% BCNU polymer) had a median survival of 23 days (P = 0.006). Group 3 (20% camptothecin polymer) had a median survival of 25 days (P = 0.023). Group 4 (50% camptothecin polymer) had a median survival of 69 days (P < 0.001). Drug loadings of 20% and 50% camptothecin released intact camptothecin for up to 1000 h in vitro. We conclude that the biodegradable polymer p(CPP: SA) releases camptothecin-sodium, produces tumoricidal tissue levels, results in little or no systemic toxicity, and prolongs survival in a rat glioma model.

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PubMed2003

The semi-interpenetrating polymer network matrix of fiber-reinforced composite and its effect on the surface adhesive properties.

This aim of this study was to examine the effect of further-impregnation time of polymer pre-impregnated fiber-reinforcement on polymer matrix structure of the fiber-reinforced composite (FRC) used in dental applications. In addition, shear bond strength between the FRC and veneering composite after various length of further-impregnation was studied. Polymethyl methacrylate (PMMA) pre-impregnated glass fiber-reinforcement was further-impregnated with a diacrylate monomer resin by using five lengths of further-impregnation from 10 min to 24 h. The test specimens (n=5) from each five groups were treated with the solvent tetrahydrofuran and examined with a scanning electron microscope (SEM) to determinate the existence of linear PMMA in the polymer matrix of the FRC. The same lengths of further-impregnation were used to form an adhesive substrate for veneering composite and to measure the shear bond strength (n=8). The SEM examination showed that linear PMMA-polymer and cross-linked diacrylate polymer formed two independent networks for the polymer matrix of FRC. The highest mean shear bond strength value (18.7+/-2.9 MPa) was achieved when the fiber reinforcement was further-impregnated for 24 h. The shortest further-impregnation, 10 min, resulted in the lowest mean shear bond strength (12.7+/-2.9 MPa). A correlation between increased shear bond strength and longer further-impregnation was found (0.689, p<0.001). The results revealed that linear PMMA network of the polymer matrix of the FRC remained in the structure regardless of the various lengths of the further-impregnation with diacrylate resin.

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PubMed2001

Control of conformational and interpolymer effects in conjugated polymers.

The role of conjugated polymers in emerging electronic, sensor and display technologies is rapidly expanding. In spite of extensive investigations, the intrinsic spectroscopic properties of conjugated polymers in precise conformational and spatial arrangements have remained elusive. The difficulties of obtaining such information are endemic to polymers, which often resist assembly into single crystals or organized structures owing to entropic and polydispersity considerations. Here we show that the conformation of individual polymers and interpolymer interactions in conjugated polymers can be controlled through the use of designed surfactant poly(p-phenylene-ethynylene) Langmuir films. We show that by mechanically inducing reversible conformational changes of these Langmuir monolayers, we can obtain the precise interrelationship of the intrinsic optical properties of a conjugated polymer and a single chain's conformation and/or interpolymer interactions. This method for controlling the structure of conjugated polymers and establishing their intrinsic spectroscopic properties should permit a more comprehensive understanding of fluorescent conjugated materials.

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PubMed2001

Ionic conductivity in crystalline polymer electrolytes.

Polymer electrolytes are the subject of intensive study, in part because of their potential use as the electrolyte in all-solid-state rechargeable lithium batteries. These materials are formed by dissolving a salt (for example LiI) in a solid host polymer such as poly(ethylene oxide) (refs 2, 3, 4, 5, 6), and may be prepared as both crystalline and amorphous phases. Conductivity in polymer electrolytes has long been viewed as confined to the amorphous phase above the glass transition temperature, Tg, where polymer chain motion creates a dynamic, disordered environment that plays a critical role in facilitating ion transport. Here we show that, in contrast to this prevailing view, ionic conductivity in the static, ordered environment of the crystalline phase can be greater than that in the equivalent amorphous material above Tg. Moreover, we demonstrate that ion transport in crystalline polymer electrolytes can be dominated by the cations, whereas both ions are generally mobile in the amorphous phase. Restriction of mobility to the lithium cation is advantageous for battery applications. The realization that order can promote ion transport in polymers is interesting in the context of electronically conducting polymers, where crystallinity favours electron transport.

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PubMed2006

Multicomponent semiconducting polymer systems with low crystallization-induced percolation threshold.

Blends and other multicomponent systems are used in various polymer applications to meet multiple requirements that cannot be fulfilled by a single material. In polymer optoelectronic devices it is often desirable to combine the semiconducting properties of the conjugated species with the excellent mechanical properties of certain commodity polymers. Here we investigate bicomponent blends comprising semicrystalline regioregular poly(3-hexylthiophene) and selected semicrystalline commodity polymers, and show that, owing to a highly favourable, crystallization-induced phase segregation of the two components, during which the semiconductor is predominantly expelled to the surfaces of cast films, we can obtain vertically stratified structures in a one-step process. Incorporating these as active layers in polymer field-effect transistors, we find that the concentration of the semiconductor can be reduced to values as low as 3 wt% without any degradation in device performance. This is in stark contrast to blends containing an amorphous insulating polymer, for which significant reduction in electrical performance was reported. Crystalline-crystalline/semiconducting-insulating multicomponent systems offer expanded flexibility for realizing high-performance semiconducting architectures at drastically reduced materials cost with improved mechanical properties and environmental stability, without the need to design all performance requirements into the active semiconducting polymer itself.

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PubMed2002

The first biantennary bacterial secondary cell wall polymer and its influence on S-layer glycoprotein assembly.

The cell surface of Aneurinibacillus thermoaerophilus DSM 10155 is covered with a square surface (S)-layer glycoprotein lattice. This S-layer glycoprotein, which was extracted with aqueous buffers after a freeze-thaw cycle of the bacterial cells, is the only completely water-soluble S-layer glycoprotein to be reported to date. The purified S-layer glycoprotein preparation had an overall carbohydrate content of 19%. Detailed chemical investigations indicated that the S-layer O-glycans of previously established structure accounted for 13% of total glycosylation. The remainder could be attributed to a peptidoglycan-associated secondary cell wall polymer. Structure analysis was performed using purified secondary cell wall polymer-peptidoglycan complexes. NMR spectroscopy revealed the first biantennary secondary cell wall polymer from the domain Bacteria, with the structure alpha-L-Glc p NAc-(1-->3)-beta-L-Man p NAc-(1-->4)-beta-L-Gal p NAc-(1-->3)-alpha-L-Glc p NAc-(1-->3)-beta-L-Man p NAc-(1-->4)-beta-L-Gal p NAc-(1-->3)-alpha-L-Glc p NAc-(1-->4)-[alpha-L-Glc p NAc-(1-->3)-beta-L-Man p NAc-(1-->4)-beta-L-Gal p NAc-(1-->3)-alpha-L-Glc p NAc-(1-->3)-beta-L-Man p NAc-(1-->4)-beta-L-Gal p NAc-(1-->3)-alpha-L-Glc p NAc-(1-->3)]-beta-L-Man p NAc-(1-->3)-alpha-L-Glc p NAc-(1-->3)-beta-L-Man p NAc-(1-->3)-alpha-L-Glc p NAc-(1-->3)-alpha-L-Glc p NAc-(1-->O)-PO(2)(-)-O-PO(2)(-)-(O-->6)-MurNAc- (where MurNAc is N -acetylmuramic acid). The neutral polysaccharide is linked via a pyrophosphate bond to the C-6 atom of every fourth N -acetylmuramic acid residue, in average, of the A1gamma-type peptidoglycan. In vivo, the biantennary polymer anchored the S-layer glycoprotein very effectively to the cell wall, probably due to the doubling of motifs for a proposed lectin-like binding between the polymer and the N-terminus of the S-layer protein. When the cellular support was removed during S-layer glycoprotein isolation, the co-purified polymer mediated the solubility of the S-layer glycoprotein in vitro. Initial crystallization experiments performed with the soluble S-layer glycoprotein revealed that the assembly property could be restored upon dissociation of the polymer by the addition of poly(ethylene glycols). The formed two-dimensional crystalline S-layer self-assembly products exhibited the same lattice symmetry as observed on intact bacterial cells.

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PubMed2004

Interfacial tension and wetting in colloid-polymer mixtures.

We calculate the interfacial tension and the wetting behavior in phase separated colloid-polymer mixtures both for ideal and excluded volume interacting polymers. Within the recently developed extension of the free volume theory to include polymer interactions the interfacial tension of the free interface is calculated by adding a van der Waals squared gradient term. The wetting behavior at a hard wall is calculated following a Cahn-Fisher-Nakanishi approach taking the one- and two-body colloid-wall interactions into account. Comparing results for interacting polymers with those for ideal polymers we find that for interacting polymers the interfacial tension does not increase as steeply as a function of the gas-liquid colloid density difference. Furthermore, the wetting transition shifts to higher polymer concentrations, even to above the triple line. The predictions for both the interfacial tension and the wetting are compared to recent experiments.

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PubMed2004

Comparison of molecular dynamics with hybrid continuum-molecular dynamics for a single tethered polymer in a solvent.

We compare a newly developed hybrid simulation method which combines classical molecular dynamics (MD) and computational fluid dynamics (CFD) to a simulation consisting only of molecular dynamics. The hybrid code is composed of three regions: a classical MD region, a continuum domain where the dynamical equations are solved by standard CFD methods, and an overlap domain where transport information from the other two domains is exchanged. The exchange of information in the overlap region ensures that momentum, energy, and mass are conserved. The validity of the hybrid code is demonstrated by studying a single polymer tethered to a hard wall immersed in explicit solvent and undergoing shear flow. In classical molecular dynamics simulation a great deal of computational time is devoted to simulating solvent molecules, although the solvent itself is of no direct interest. By contrast, the hybrid code simulates the polymer and surrounding solvent explicitly, whereas the solvent farther away from the polymer is modeled using a continuum description. In the hybrid simulations the MD domain is an open system whose number of particles is controlled to filter the perturbative density waves produced by the polymer motion. We compare conformational properties of the polymer in both simulations for various shear rates. In all cases polymer properties compare extremely well between the two simulation scenarios, thereby demonstrating that this hybrid method is a useful way to model a system with polymers and under nonzero flow conditions. There is also good agreement between the MD and hybrid schemes and experimental data on tethered DNA in flow. The computational cost of the hybrid protocol can be reduced to less than 6% of the cost of updating the MD forces, confirming the practical value of the method.

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PubMed2004

Semiflexible polymers in a random environment.

We present using simple scaling arguments and one step replica symmetry breaking a theory for the localization of semiflexible polymers in a quenched random environment. In contrast to completely flexible polymers, localization of semiflexible polymers depends not only on the details of the disorder but also on the ease with which polymers can bend. The interplay of these two effects can lead to the delocalization of a localized polymer with an increase in either the disorder density or the stiffness. Our theory provides a general criterion for the delocalization of polymers with varying degrees of flexibility and allows us to propose a phase diagram for the highly folded (localized) states of semiflexible polymers as a function of the disorder strength and chain rigidity.

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