Polymers

Polymers, Vol. 4, Pages 486-500: Enzymatic Synthesis and Crosslinking of Novel High Molecular Weight Polyepoxyricinoleate

Ayaki Kazariya — Fri, 10 Feb 2012 00:00:00 CET

Methyl epoxyricinoleate was prepared in high yield by the lipase-catalyzed epoxidation of methyl ricinoleate with H2O2. A high molecular weight polyepoxyricinoleate (PER) with a maximum weight average molecular weight (Mw) of 272,000 was enzymatically prepared by the polycondensation of methyl epoxyricinoleate using immobilized lipase from Burkholderia cepacia (lipase PS-IM) in bulk at 80 °C for 5 d. PER showed good low temperature fluidability. PER was readily cured by maleic anhydride (MA) at 80 °C to produce a chloroform-insoluble PER-MA film. Both the glass transition temperature and Young’s modulus increased with increasing MA content and PER Mw. In contrast, the elongation at break decreased with increasing MA content and PER Mw. Methyl epoxyricinoleate, PER and PER-MA showed biodegradability by activated sludge, and that of the PER-MA film decreased with increasing MA content.

Polymers, Vol. 4, Pages 463-485: Multiscale Modeling for Host-Guest Chemistry of Dendrimers in Solution

Seung Ha Kim — Fri, 10 Feb 2012 00:00:00 CET

Dendrimers have been widely used as nanostructured carriers for guest species in a variety of applications in medicine, catalysis, and environmental remediation. Theory and simulation methods are an important complement to experimental approaches that are designed to develop a fundamental understanding about how dendrimers interact with guest molecules. This review focuses on computational studies aimed at providing a better understanding of the relevant physicochemical parameters at play in the binding and release mechanisms between polyamidoamine (PAMAM) dendrimers and guest species. We highlight recent contributions that model supramolecular dendrimer-guest complexes over the temporal and spatial scales spanned by simulation methods ranging from all-atom molecular dynamics to statistical field theory. The role of solvent effects on dendrimer-guest interactions and the importance of relating model parameters across multiple scales is discussed.

Polymers, Vol. 4, Pages 448-462: In Situ and Ex Situ Syntheses of Magnetic Liquid Crystalline Materials: A Comparison

Ophelie Riou — Fri, 10 Feb 2012 00:00:00 CET

Magnetic hybrid liquid crystalline composites have been obtained either by thermal decomposition of a cobalt precursor in a solution containing a liquid crystal polymer or by dispersing preformed cobalt nanorods in a liquid crystal polymer matrix. The final materials are all mesomorphous and ferromagnetic. Their magnetic characteristics are compared as a function of the synthesis method.

Polymers, Vol. 4, Pages 408-447: Polysilane Dendrimers

Clemens Krempner — Thu, 09 Feb 2012 00:00:00 CET

The synthesis, structure and electronic properties of polysilane dendrimers, a relatively new class of highly branched and silicon-rich molecular architectures is reviewed. After a detailed discussion of main synthetic strategies to well-defined single-core and double-core polysilane dendrimers, important structural and conformational features determined by single crystal X-ray crystallography and 29Si-NMR spectroscopy are presented. The last part highlights the most interesting photochemical properties of polysilane dendrimers such as UV absorption and emission behavior, which are compared with those of linear and branched polysilanes.

Polymers, Vol. 4, Pages 396-407: Degree of Branching in Hyperbranched Poly(glycerol-co-diacid)s Synthesized in Toluene

Victor T. Wyatt — Mon, 06 Feb 2012 00:00:00 CET

1H NMR and 13C NMR spectrometry (1-dimensional and 2-dimensional) have been used to assign chemical resonances and determine the degrees of branching for polyesters synthesized by the Lewis acid (dibutyltin(IV)oxide)-catalyzed polycondensation of glycerol with either succinic acid (n (aliphatic chain length) = 2), glutaric acid (n = 3) or azelaic acid (n = 7) in quasi-melt solutions with toluene. When 1:1 and 2:1 (diacid:glycerol) molar ratios were used, it was found that the glutaric acid-derived polymers gave the highest degree of polymer branching (31.2%, 85.6%, respectively) after the 24 h reaction period followed by the succinic acid-derived polymers (39.4%, 41.9%, respectively) and the azelaic acid-derived polymers (9.9%, 13.9%, respectively). Reactions performed at reflux for 24 h resulted in a 70.8% and 56.7% decrease in degree of branching for succinic acid and glutaric acid-derived polyesters, respectively. There is no indication that degree of branching is significantly affected by the presence or absence of solvent according to the results obtained in this research.

Polymers, Vol. 4, Pages 355-395: Dendronization: A Useful Synthetic Strategy to Prepare Multifunctional Materials

Julieta I. Paez — Thu, 02 Feb 2012 00:00:00 CET

Dendronization is a synthetic methodology that offers important advantages. The resulting products, which are called dendronized materials, present new and specific properties. This review shows numerous examples in which individual dendrons are used as building blocks to prepare more complex arrays via covalent or non-covalent interactions. In particular, it points out how the structural information programmed into the dendritic architecture can be used in the dendronization process to generate nanostructures with specific tailored properties. We emphasize the use of different dendrons, with diverse chemical structure and size, to functionalize diverse substrates like linear polymers, and plane and curved inorganic surfaces. Apart from this, the review also demonstrates that self-assembly represents an ideal approach to create well-defined hyperbranched surfaces and it includes some discussion about the ability of both organic and inorganic building blocks to direct this process.

Polymers, Vol. 4, Pages 341-354: Effects of Emulsion-Based Resonant Infrared Matrix Assisted Pulsed Laser Evaporation (RIR-MAPLE) on the Molecular Weight of Polymers

Ryan D. McCormick — Wed, 01 Feb 2012 00:00:00 CET

The molecular weight of a polymer determines key optoelectronic device characteristics, such as internal morphology and charge transport. Therefore, it is important to ensure that polymer deposition techniques do not significantly alter the native polymer molecular weight. This work addresses polymers deposited by resonant infrared matrix-assisted pulsed laser evaporation (RIR-MAPLE). By using a novel emulsion-based target technique, the deposition of smooth, contiguous films with no evidence of chemical degradation have been enabled. However, structural degradation via a reduction in molecular weight remains an open question. The common polymer standard, PMMA, and the optoelectronic polymers, P3HT and MEH-PPV, have been characterized before and after emulsion-based RIR-MAPLE deposition via gel permeation chromatography to determine if RIR-MAPLE affects the deposited polymer molecular weight. Proton nuclear magnetic resonance spectroscopy and Fourier transform infrared spectroscopy measurements have also been conducted to verify the absence of chemical degradation. These measurements verify that there is no chemical degradation of the polymers, and that PMMA and P3HT show no structural degradation, but MEH-PPV exhibits a halving of the weight-averaged molecular weight after RIR-MAPLE deposition. Compared with competing laser deposition techniques, RIR-MAPLE is shown to have the least effect on the molecular weight of the resulting thin films.

Polymers, Vol. 4, Pages 316-340: Nanoparticle-Liquid Crystalline Elastomer Composites

Yan Ji — Mon, 30 Jan 2012 00:00:00 CET

Liquid crystalline elastomers (LCEs) exhibit a number of remarkable physical effects, including a uniquely high-stroke reversible mechanical actuation triggered by external stimuli. Fundamentally, all such stimuli affect the degree of liquid crystalline order in the polymer chains cross-linked into an elastic network. Heat and the resulting thermal actuation act by promoting entropic disorder, as does the addition of solvents. Photo-isomerization is another mechanism of actuation, reducing the orientational order by diminishing the fraction of active rod-like mesogenic units, mostly studied for azobenzene derivatives incorporated into the LCE composition. Embedding nanoparticles provides a new, promising strategy to add functionality to LCEs and ultimately enhance their performance as sensors and actuators. The motivation for the combination of nanoparticles with LCEs is to provide better-controlled actuation stimuli, such as electric and magnetic fields, and broad-spectrum light, by selecting and configuring the appropriate nanoparticles in the LCE matrix. Here we give an overview of recent advances in this area with a focus on preparation, physical properties and actuation performance of the resultant nanocomposites.

Polymers, Vol. 4, Pages 296-315: Selective Grafting of Primary Amines onto Carbon Nanotubes via Free-Radical Treatment in Microwave Plasma Post-Discharge

Benoit Ruelle — Mon, 30 Jan 2012 00:00:00 CET

A novel strategy to graft functional groups at the surface of carbon nanotubes (CNTs) is discussed. Aiming at grafting nitrogen containing groups, and more specifically primary amine covalent functionalization, CNTs were exposed under atomic nitrogen flow arising from an Ar + N2 microwave plasma. The primary amine functions were identified and quantified through chemical derivatization with 4-(trifluoromethyl)benzaldehyde and characterized through X-ray photoelectron spectroscopy. The increase of the selectivity in the primary amines grafting onto CNTs, up to 66.7% for treatment of CNT powder, was performed via the reduction of post-treatment oxygen contamination and the addition of hydrogen in the experimental set-up, more particularly in the plasma post-discharge chamber. The analyses of nitrogenated and primary amine functions grafting on the CNT surface suggest that atomic nitrogen (N•) and reduced nitrogen species (NH• and NH2•) react preferentially with defect sites of CNTs and, then, only atomic nitrogen continues to react on the CNT surface, creating defects.

Polymers, Vol. 4, Pages 275-295: Dispersion of Carbon Nanotubes: Mixing, Sonication, Stabilization, and Composite Properties

Yan Yan Huang — Mon, 23 Jan 2012 00:00:00 CET

Advances in functionality and reliability of carbon nanotube (CNT) composite materials require careful formulation of processing methods to ultimately realize the desired properties. To date, controlled dispersion of CNTs in a solution or a composite matrix remains a challenge, due to the strong van der Waals binding energies associated with the CNT aggregates. There is also insufficiently defined correlation between the microstructure and the physical properties of the composite. Here, we offer a review of the dispersion processes of pristine (non-covalently functionalized) CNTs in a solvent or a polymer solution. We summarize and adapt relevant theoretical analysis to guide the dispersion design and selection, from the processes of mixing/sonication, to the application of surfactants for stabilization, to the final testing of composite properties. The same approaches are expected to be also applicable to the fabrication of other composite materials involving homogeneously dispersed nanoparticles.

Polymers, Vol. 4, Pages 256-274: Shrinkage Characteristics of Experimental Polymer Containing Composites under Controlled Light Curing Modes

Alain Pefferkorn — Wed, 18 Jan 2012 00:00:00 CET

The adsorption of polymethylmethacrylate polymer of different molecular weight at the aerosil/ethyleneglycol- or 1,3 butanediol-dimethacrylate interfaces was determined to provide microstructured networks. Their structural characteristics were determined to be controlled by the amount of polymer initially supplied to the system. The sediment (the settled phase) characteristics, determined as a function of the polymer concentration and the rate of the polymerization shrinkage determined for composite resins, obtained by extrusion of the sediment after centrifugation, were found to be correlated. The specific role of the adsorbed polymer was found to be differently perturbed with the supplementary supply of dimethacrylate based monomer additives. Particularly, the bisphenol A dimethacrylate that generated crystals within the sediment was found to impede the shrinkage along the crystal lateral faces and strongly limit the shrinkage along its basal faces. Addition of ethyleneglycol- or polyethylene-glycoldimethacrylate monomers was determined to modify the sedimentation characteristics of the aerosil suspension and the shrinkage properties of the composites. Finally, the effects of stepwise light curing methods with prolonged lighting-off periods were investigated and found to modify the development and the final values of the composite shrinkage.

Polymers, Vol. 4, Pages 240-255: Conformational Effects in Non-Stoichiometric Complexes of Two Hyperbranched Molecules with a Linear Polyelectrolyte

George Dalakoglou — Tue, 17 Jan 2012 00:00:00 CET

We report results from Brownian dynamics computer simulations of systems comprised by two terminally charged hyperbranched molecules preferentially branched in the periphery, with an oppositely charged linear chain of varying length. Comparison of the findings from the present study to stoichiometric counterparts and to analogous dendrimer-based complexes, reveal that the presence of the second hyperbranched molecule incurs significant changes in the conformational characteristics of both components of the complex. Instead of step-like changes in the average size and shape of the hyperbranched component that were noted in the previously studied stoichiometric systems, a rather smooth change is observed upon increase of the length of the linear component. In addition, a markedly different behavior is also noticed in the conformational characteristics of the linear chain when compared to that in similar dendrimer-based systems. The above findings are consistent with the higher degree of deformability of the peripherally branched molecules which allow appropriate rearrangements in shape in order to accommodate the favorable Coulombic interactions between the two components of the complex. This behavior offers new insight towards the design of more efficient hyperbranched-based systems which can take advantage of the multifunctionality and the structural properties of the highly branched polymer components.

Polymers, Vol. 4, Pages 211-239: Internal Dynamics of Dendritic Molecules Probed by Pyrene Excimer Formation

Jean Duhamel — Tue, 17 Jan 2012 00:00:00 CET

This review exposes the current poor understanding of the internal segmental chain dynamics of dendrimers in solution probed by monitoring the process of excimer formation between pyrene labels covalently attached to the chain ends of dendrimers. The review begins by covering the bases of fluorescence and the kinetics of pyrene excimer formation before describing a procedure based on the Model Free (MF) analysis that is used to analyze quantitatively the fluorescence decays acquired for dendrimers, the ends of which have been fully and covalently labeled with pyrene. Comparison of the various trends obtained by different research groups describing the efficiency of pyrene excimer formation with the generation number of dendrimers illustrates the lack of consensus between the few studies devoted to the topic. One possible reason for this disagreement might reside in the presence of minute amounts of unattached pyrene labels which act as potent fluorescent impurities and affect the analysis of the fluorescence spectra and decays in an uncontrolled manner. The review points out that the MF analysis of the fluorescence decays acquired with pyrene-labeled dendrimers enables one to account for the presence of unattached pyrene and to retrieve information about the internal segmental dynamics of the dendrimer. It provides guidelines that should enable future studies on pyrene-labeled dendrimers to yield results that are more straightforward to interpret.

Polymers, Vol. 4, Pages 187-210: The Mechanical Properties of Epoxy Composites Filled with Rubbery Copolymer Grafted SiO2

Jianing Gao — Mon, 16 Jan 2012 00:00:00 CET

This study demonstrated a method for toughening a highly crosslinked anhydride cured DGEBA epoxy using rubbery block copolymer grafted SiO2 nanoparticles. The particles were synthesized by a sequential reversible addition-fragmentation chain transfer (RAFT) polymerization. The inner rubbery block poly(n-hexyl methacrylate) (PHMA) had a glass transition temperature below room temperature. The outer block poly(glycidyl methacrylate) (PGMA) was matrix compatible. A rubbery interlayer thickness of 100% and 200% of the particle core radius was achieved by grafting a 20 kg/mol and a 40 kg/mol PHMA at a graft density of 0.7 chains/nm2 from the SiO2 surface. The 20 kg/mol rubbery interlayer transferred load more efficiently to the SiO2 cores than the 40 kg/mol rubbery interlayer and maintained the epoxy modulus up to a loading of 10 vol% of the rubbery interlayer. Both systems enabled cavitation or plastic dilatation. Improvement of the strain-to-break and the tensile toughness was found in both systems. We hypothesize that plastic void growth in the matrix is the primary mechanism causing the improvement of the ductility.

Polymers, Vol. 4, Pages 150-186: Optical and Physical Applications of Photocontrollable Materials: Azobenzene-Containing and Liquid Crystalline Polymers

Akira Emoto — Mon, 09 Jan 2012 00:00:00 CET

Photocontrol of molecular alignment is an exceptionally-intelligent and useful strategy. It enables us to control optical coefficients, peripheral molecular alignments, surface relief structure, and actuation of substances by means of photoirradiation. Azobenzene-containing polymers and functionalized liquid crystalline polymers are well-known photocontrollable materials. In this paper, we introduce recent applications of these materials in the fields of mechanics, self-organized structuring, mass transport, optics, and photonics. The concepts in each application are explained based on the mechanisms of photocontrol. The interesting natures of the photocontrollable materials and the conceptual applications will stimulate novel ideas for future research and development in this field.

Polymers, Vol. 4, Pages 134-149: Color-Tunable Etalons Assembled from Poly (N-Isopropylacrylamide) Based Microgels

Liang Hu — Mon, 09 Jan 2012 00:00:00 CET

Photonic materials (PMs) that are capable of manipulating and controlling light in systems have immense potential for the computing and communications industries. These materials are formed by assembling components of differing refractive indices in a periodic array. Light then interacts with this assembly, which results in constructive and destructive interference, and hence color. While many three-dimensional PMs have been reported, and have the most potential for the applications mentioned above, one-dimensional PMs have a multitude of potential uses, e.g., light filtration. In this review, we focus on one-dimensional PMs; specifically poly (N-isopropylacrylamide) microgel based etalons. The etalons can be fabricated to exhibit a single bright color, and because the diameter of the microgels is dependent on temperature and pH, the mirror-mirror spacing can be dynamically tuned; therefore the etalon’s color is dynamically tunable.

Polymers, Vol. 4, Pages 116-133: Preparation and Applications of Amylose Supramolecules by Means of Phosphorylase-Catalyzed Enzymatic Polymerization

Jun-ichi Kadokawa — Mon, 09 Jan 2012 00:00:00 CET

This paper reviews preparation and applications of amylose supramolecules by means of phosphorylase-catalyzed enzymatic polymerization. When the enzymatic polymerization of α-d-glucose 1-phosphate (G-1-P) as a monomer was carried out in the presence of poly(tetrahydrofuran) (PTHF) of a hydrophobic polyether as a guest polymer, the supramolecule, i.e., an amylose-PTHF inclusion complex, was formed in the process of polymerization. Because the representation of propagation in the polymerization is similar to the way that vines of plants grow twining around rods, this polymerization method for the preparation of amylose-polymer inclusion complexes was proposed to be named “vine-twining polymerization”. Various hydrophobic polyethers, polyesters, poly(ester-ether), and polycarbonates were also employed as the guest polymer in the vine-twining polymerization to produce the corresponding inclusion complexes. To obtain the inclusion complex from a strongly hydrophobic guest polymer, the parallel enzymatic polymerization system was developed as an advanced extension of the vine-twining polymerization. In addition, it was found that amylose selectively includes one side of the guest polymer from a mixture of two resemblant guest polymers, as well as a specific range in molecular weights of the guest PTHF. Amylose also exhibited selective inclusion behavior toward stereoisomers of poly(lactide)s. Moreover, the preparation of hydrogels through the formation of inclusion complexes of amylose in vine-twining polymerization was achieved.

Polymers, Vol. 4, Pages 72-115: Phase Diagrams for Systems Containing Hyperbranched Polymers

Sabine Enders — Mon, 09 Jan 2012 00:00:00 CET

Hyperbranched polymers show an outstanding potential for applications ranging from chemistry over nanotechnology to pharmacy. In order to take advantage of this potential, the underlying phase behaviour must be known. From the thermodynamic point of view, the modelling of these phase diagrams is quite challenging, because the thermodynamic properties depend on the architecture of the hyperbranched polymer as well as on the number and kind of present functional end groups. The influence of architecture can be taken into account via the lattice cluster theory (LCT) as an extension of the well-known Flory–Huggins theory. Whereas the Flory–Huggins theory is limited to linear polymer chains, the LCT can be applied to an arbitrary chain architecture. The number and the kind of functional groups can be handled via the Wertheim perturbation theory, applicable for directed forces between the functional groups and the surrounding solvent molecules. The combination of the LCT and the Wertheim theory can be established for the modelling or even prediction of the liquid-liquid equilibria (LLE) of polymer solutions in a single solvent or in a solvent mixture or polymer blends, where the polymer can have an arbitrary structure. The applied theory predicts large demixing regions for mixtures of linear polymers and hyperbranched polymers, as well as for mixtures made from two hyperbranched polymers. The introduction of empty lattice sites permits the theoretical investigation of pressure effects on phase behaviour. The calculated phase diagrams were compared with own experimental data or to experimental data taken from literature.

Polymers, Vol. 4, Pages 46-71: Antimicrobial Polymers in Solution and on Surfaces: Overview and Functional Principles

Felix Siedenbiedel — Mon, 09 Jan 2012 00:00:00 CET

The control of microbial infections is a very important issue in modern society. In general there are two ways to stop microbes from infecting humans or deteriorating materials—disinfection and antimicrobial surfaces. The first is usually realized by disinfectants, which are a considerable environmental pollution problem and also support the development of resistant microbial strains. Antimicrobial surfaces are usually designed by impregnation of materials with biocides that are released into the surroundings whereupon microbes are killed. Antimicrobial polymers are the up and coming new class of disinfectants, which can be used even as an alternative to antibiotics in some cases. Interestingly, antimicrobial polymers can be tethered to surfaces without losing their biological activity, which enables the design of surfaces that kill microbes without releasing biocides. The present review considers the working mechanisms of antimicrobial polymers and of contact-active antimicrobial surfaces based on examples of recent research as well as on multifunctional antimicrobial materials.

Polymers, Vol. 4, Pages 32-45: Solution Properties of Water-Soluble “Smart” Poly(N-acryloyl-N′-ethyl piperazine-co-methyl methacrylate)

G. Roshan Deen — Thu, 05 Jan 2012 00:00:00 CET

Water-soluble copolymers of N-acryloyl-N′-ethylpiperazine (AcrNEP) with methyl methacrylate (MMA) were synthesized to high conversion by free-radical solution polymerization. The composition of the copolymers was determined using Fourier Transform Infra-red Spectroscopy (FTIR). Copolymers containing AcrNEP content above 44 mol% were readily soluble in water and exhibited the critical solution temperature behavior. The copolymers were strongly responsive to changes in pH of the external medium due to the presence of tertiary amine functions that could be protonated at low pH. The influence of various factors such as copolymer composition, pH, temperature, salt and surfactant concentration on the LCST of the copolymers were systematically studied. The intrinsic viscosity of the copolymers in dimethyl formamide decreased with increase in temperature due to a decrease in thermodynamic affinity between polymer chains and solvent molecules. The viscosity behavior of the copolymers in sodium chloride solution was similar to that of classical polyelectrolytes and hydrophobically modified polyacrylate systems.

Polymers, Vol. 4, Pages 20-31: Hydrodynamic Behavior of Dendrigraft Polylysines in Water and Dimethylformamide

Natalia Yevlampieva — Mon, 02 Jan 2012 00:00:00 CET

The four first generations of dendrigraft poly-L-lysine have been studied in dimethylformamide (aprotic solvent) and in 0.2 M NaCl aqueous solutions by isothermal translation diffusion, 1H NMR and viscometry methods. The relationships between diffusion coefficient, intrinsic viscosity and molar mass have been determined for dendrigraft poly-L-lysines, and the scaling index values have been compared to classical trifunctional dendrimers. Dendrimers and dendrigraft poly-L-lysines exhibited similitudes in their hydrodynamic behaviors. Nevertheless, dendrigraft poly-L-lysines displayed a specific behavior in solution. In contrast to dendrimers, a significant change of hydrodynamic dimension of dendrigraft poly-L-lysines according to the nature of the solvent has been observed. In aprotic solvent, the dendrigraft poly-L-lysine dimensions are about two times lower than in aqueous media (i.e., the hydrodynamic volume is contracted by a factor 8 in dimethylformamide), revealing the softness of dendrigraft poly-L-lysine compared to classical trifunctional dendrimers.

Polymers, Vol. 4, Pages 1-19: Polymer-Nanocrystal Hybrid Materials for Light Conversion Applications

Ying Yuan — Tue, 27 Dec 2011 00:00:00 CET

In this mini-review we report on current developments of hybrid materials based on semiconductor nanocrystals integrated into polymer matrices for direct light conversion, their present limitations, as well as their high potential for future applications.

Polymers, Vol. 3, Pages 2156-2171: Experimentally Justified Model-Like Description of Consolidation of Precipitated Silica

Hussein Sahabi — Tue, 20 Dec 2011 00:00:00 CET

Colloidal gels are intermediates in the production of highly porous particle systems. In the production process, the gels are fragmented after their creation. These gel fragments consolidate to particles whose application-technological properties are determined by their size and porosity. A model of the consolidation process is proposed: The consolidation process of a gel fragment is simulated with the Molecular Dynamics (MD) method with the assumption of van der Waals forces in interplay with the thermal motion as driving forces for the consolidation. The simulation results are compared with experimental data and with a Monte Carlo (MC) simulation.

Polymers, Vol. 3, Pages 2142-2155: Plasma Treated Multi-Walled Carbon Nanotubes (MWCNTs) for Epoxy Nanocomposites

Andrew C. Ritts — Mon, 19 Dec 2011 00:00:00 CET

Plasma nanocoating of allylamine were deposited on the surfaces of multi-walled carbon nanotubes (MWCNTs) to provide desirable functionalities and thus to tailor the surface characteristics of MWCNTs for improved dispersion and interfacial adhesion in epoxy matrices. Plasma nanocoated MWCNTs were characterized using scanning electron microscopy (SEM), high-resolution transmission electron microscopy (HR-TEM), surface contact angle, and pH change measurements. Mechanical testing results showed that epoxy reinforced with 1.0 wt % plasma coated MWCNTs increased the tensile strength by 54% as compared with the pure epoxy control, while epoxy reinforced with untreated MWCNTs have lower tensile strength than the pure epoxy control. Optical and electron microscopic images show enhanced dispersion of plasma coated MWCNTs in epoxy compared to untreated MWCNTs. Plasma nanocoatings from allylamine on MWCNTs could significantly enhance their dispersion and interfacial adhesion in epoxy matrices. Simulation results based on the shear-lag model derived from micromechanics also confirmed that plasma nanocoating on MWCNTs significantly improved the epoxy/fillers interface bonding and as a result the increased composite strength.

Polymers, Vol. 3, Pages 2133-2141: Design of Improved Metal-Organic Framework (MOF) H2 Adsorbents

Terumi Furuta — Mon, 12 Dec 2011 00:00:00 CET

We attempted synthesis of the hydrogen adsorption material suitable for the fuel cell vehicles (FCEVs). The designed and synthesized Cu2(3,5-Pyridinedicarboxylate)2 (=Cu2PDC2) metal complex showed an extremely high volumetric uptake density for a physisorption material, even though the specific surface area was only about 1,000 m2 g−1. Factors for high uptake properties are considered to be the increased adsorption sites per unit area, the increased adsorption energy, and the optimized design of pore shapes. High hydrogen uptake on volumetric basis is especially effective for FCEV because the tank volume is reduced. It is expected that property prediction using computational simulation and sophisticated analysis at the micro and nano levels will become an indispensable tool in the design of functional materials.

Polymers, Vol. 3, Pages 2107-2132: Water Soluble Responsive Polymer Brushes

Michael P. Weir — Wed, 07 Dec 2011 00:00:00 CET

Responsive polymer brushes possess many interesting properties that enable them to control a range of important interfacial behaviours, including adhesion, wettability, surface adsorption, friction, flow and motility. The ability to design a macromolecular response to a wide variety of external stimuli makes polymer brushes an exciting class of functional materials, and has been made possible by advances in modern controlled polymerization techniques. In this review we discuss the physics of polymer brush response along with a summary of the techniques used in their synthesis. We then review the various stimuli that can be used to switch brush conformation; temperature, solvent quality, pH and ionic strength as well as the relatively new area of electric field actuation We discuss examples of devices that utilise brush conformational change, before highlighting other potential applications of responsive brushes in real world devices.

Polymers, Vol. 3, Pages 2088-2106: Effects of D-Lysine Substitutions on the Activity and Selectivity of Antimicrobial Peptide CM15

Heather M. Kaminski — Tue, 06 Dec 2011 00:00:00 CET

Despite their potent antimicrobial activity, the usefulness of antimicrobial peptides (AMPs) as antibiotics has been limited by their toxicity to eukaryotic cells and a lack of stability in vivo. In the present study we examined the effects of introducing D-lysine residues into a 15-residue hybrid AMP containing residues 1–7 of cecropin A and residues 2–9 of melittin (designated CM15). Diastereomeric analogs of CM15 containing between two and five D-lysine substitutions were evaluated for their antimicrobial activity, lysis of human erythrocytes, toxicity to murine macrophages, ability to disrupt cell membranes, and protease stability. All of the analogs caused rapid permeabilization of the Staphylococcus aureus cell envelope, as indicated by uptake of SYTOX green. Permeabilization of the plasma membrane of RAW264.7 macrophages was also observed for CM15, but this was substantially diminished for the D-lysine containing analogs. The introduction of D-lysine caused moderate decreases in antimicrobial activity for all analogs studied, with a much more pronounced reduction in toxicity to eukaryotic cells, leading to marked improvements in antimicrobial efficacy. Circular dichroism studies indicated a progressive loss of helical secondary structure upon introduction of D-lysine residues, with a good correspondence between helical content and eukaryotic cell cytotoxicity. Overall, these studies indicate that disruption of amphipathic secondary structure reduces both antimicrobial activity and eukaryotic cell toxicity, but that the reduction in eukaryotic cell cytotoxicity is more pronounced, leading to an overall gain in antimicrobial selectivity.

Polymers, Vol. 3, Pages 2078-2087: Embryonic Stem Cells Maintain an Undifferentiated State on Dendrimer-Immobilized Surface with d-Glucose Display

Shohreh Mashayekhan — Mon, 05 Dec 2011 00:00:00 CET

In serial passaging cultures of mouse embryonic stem (ES) cells, we employed a dendrimer-immobilized substrate that displayed d-glucose as a terminal ligand. The d-glucose-displaying dendrimer (GLU/D) surface caused the ES cells to form loosely attached spherical colonies, while those on a gelatin-coated surface formed flatter colonies that were firmly attached to the surface. Despite the morphological similarities between the colonies on the GLU/D surface and aggregates on a conventional bacteriological dish, immunostaining and RT-PCR analyses revealed the maintenance of cells within the spherical colonies on the GLU/D surface in an undifferentiated state with very low expressions of primitive endoderm markers. On the bacteriological dish, however, the cells within the aggregates showed a different cellular state with partial differentiation into the primitive endoderm lineage, and the expression level increased gradually along with the number of passages. These results indicate that the GLU/D surface can be a potential tool for controlling the ES cell morphology and then govern their self-renewal and fate.

Polymers, Vol. 3, Pages 2053-2077: Mechanisms of Light Energy Harvesting in Dendrimers and Hyperbranched Polymers

David S. Bradshaw — Mon, 05 Dec 2011 00:00:00 CET

Since their earliest synthesis, much interest has arisen in the use of dendritic and structurally allied forms of polymer for light energy harvesting, especially as organic adjuncts for solar energy devices. With the facility to accommodate a proliferation of antenna chromophores, such materials can capture and channel light energy with a high degree of efficiency, each polymer unit potentially delivering the energy of one photon—or more, when optical nonlinearity is involved. To ensure the highest efficiency of operation, it is essential to understand the processes responsible for photon capture and channelling of the resulting electronic excitation. Highlighting the latest theoretical advances, this paper reviews the principal mechanisms, which prove to involve a complex interplay of structural, spectroscopic and electrodynamic properties. Designing materials with the capacity to capture and control light energy facilitates applications that now extend from solar energy to medical photonics.

Polymers, Vol. 3, Pages 2039-2052: The Influence of Synthesis Parameters on Particle Size and Photoluminescence Characteristics of Ligand Capped Tb3+:LaF3

Kyle Gipson — Tue, 29 Nov 2011 00:00:00 CET

Organic ligand surface-treated Tb3+:LaF3 was synthesized in water and methanol for subsequent incorporation into polymethyl methacrylate (PMMA) via solution-precipitation chemistry in order to produce optically active polymer nanocomposites. Nanoparticle agglomerate diameters ranged from 388 ± 188 nm when synthesized in water and 37 ± 2 nm when synthesized in methanol. Suspension stability is paramount for producing optically transparent materials. Methanol nanoparticle synthesized at a pH of 3 exhibited the smallest agglomerate size. Optical spectroscopy, dynamic light scattering, transmission electron microscopy, scanning transmission electron microscopy, and zeta potential analysis were used to characterize the particles synthesized.

Polymers, Vol. 3, Pages 2018-2038: Incorporation of Hyperbranched Supramolecules into Nafion Ionic Domains via Impregnation and In-Situ Photopolymerization

Nadzrinahamin A. Nazir — Mon, 28 Nov 2011 00:00:00 CET

Nafion membranes were impregnated with photocurable supramolecules, viz., hyperbranched polyester having pendant functional carboxylic acid groups (HBPEAc-COOH) by swelling in methanol and subsequently photocured in-situ after drying. Structure-property relationships of the HBPEAc-COOH impregnated Nafion membranes were analyzed on the basis of Fourier transform infrared (FTIR) spectroscopy, solid-state nuclear magnetic resonance (SSNMR) and dynamic mechanical analysis (DMA). FTIR and SSNMR investigations revealed that about 7 wt % of HBPEAc-COOH was actually incorporated into the ionic domains of Nafion. The FTIR study suggests possible complexation via inter-species hydrogen bonding between the carboxylic groups of HBPEAc-COOH and the sulfonate groups of Nafion. The α-relaxation peak corresponding to the glass transition temperature of the ionic domains of the neat Nafion-acid form was found to increase from ~100 to ~130 °C upon impregnation with enhanced modulus afforded by the cured polyester network within the ionic domains. The AC impedance fuel cell measurement of the impregnated membrane exhibited an increasing trend of proton conductivity with increasing temperature, which eventually surpassed that of neat Nafion above 100 °C. Of particular importance is that the present paper is the first to successfully incorporate polymer molecules/networks into the Nafion ionic domains by means of impregnation with hyperbranched supramolecules followed by in-situ photopolymerization.

Polymers, Vol. 3, Pages 2010-2017: Role of Antimicrobial Peptides in Inflammatory Bowel Disease

Jan-Michel Otte — Wed, 16 Nov 2011 00:00:00 CET

Inflammatory bowel diseases (IBD) are characterized by a chronic relapsing inflammation of the gastrointestinal mucosa. The etiology and pathogenesis of these disorders such as Crohn’s disease and ulcerative colitis are incompletely understood. Recently, antimicrobial peptides, which are expressed by leukocytes and epithelia, have been implicated in the pathogenesis of IBD. Antimicrobial peptides are pivotal for intestinal defense, shaping the composition of the luminal flora and contributing thereby to the maintenance of intestinal homeostasis. Apart from their antimicrobial activity affecting commensal bacteria, immunomodulatory properties of antimicrobial peptides have been identified, which link innate and adaptive immune response. There is increasing evidence that alterations in mucosal levels of these peptides contribute to IBD pathogenensis.

Polymers, Vol. 3, Pages 1972-2009: Water Soluble Polymers for Pharmaceutical Applications

Veeran Gowda Kadajji — Fri, 11 Nov 2011 00:00:00 CET

Advances in polymer science have led to the development of novel drug delivery systems. Some polymers are obtained from natural resources and then chemically modified for various applications, while others are chemically synthesized and used. A large number of natural and synthetic polymers are available. In the present paper, only water soluble polymers are described. They have been explained in two categories (1) synthetic and (2) natural. Drug polymer conjugates, block copolymers, hydrogels and other water soluble drug polymer complexes have also been explained. The general properties and applications of different water soluble polymers in the formulation of different dosage forms, novel delivery systems and biomedical applications will be discussed.

Polymers, Vol. 3, Pages 1944-1971: Threshold Particle Diameters in Miniemulsion Reversible-Deactivation Radical Polymerization

Hidetaka Tobita — Fri, 11 Nov 2011 00:00:00 CET

Various types of controlled/living radical polymerizations, or using the IUPAC recommended term, reversible-deactivation radical polymerization (RDRP), conducted inside nano-sized reaction loci are considered in a unified manner, based on the polymerization rate expression, Rp = kp[M]K[Interm]/[Trap]. Unique miniemulsion polymerization kinetics of RDRP are elucidated on the basis of the following two factors: (1) A high single molecule concentration in a nano-sized particle; and (2) a significant statistical concentration variation among particles. The characteristic particle diameters below which the polymerization rate start to deviate significantly (1) from the corresponding bulk polymerization, and (2) from the estimate using the average concentrations, can be estimated by using simple equations. For stable-radical-mediated polymerization (SRMP) and atom-transfer radical polymerization (ATRP), an acceleration window is predicted for the particle diameter range, . For reversible-addition-fragmentation chain-transfer polymerization (RAFT), degenerative-transfer radical polymerization (DTRP) and also for the conventional nonliving radical polymerization, a significant rate increase occurs for . On the other hand, for the polymerization rate is suppressed because of a large statistical variation of monomer concentration among particles.

Polymers, Vol. 3, Pages 1934-1943: Synthesis and Characterization of Novel Copper(II) 2D Coordination Polymers from a Fluorinated Flexible Ligand with Remarkable Clathration Ability

Tomohiro Beni — Mon, 07 Nov 2011 00:00:00 CET

Two-dimensional (2D) grid coordination polymers were prepared by the reaction of 1,4-bis(4-pyridylmethyl)tetrafluorobenzene (bpf) with Cu(NO3)2 in the presence of aromatic compounds. Crystal structures of {[Cu(bpf)2(NO3)2]·(biphenyl)2}n (1), {[Cu(bpf)2(NO3)2]·(m-C6H4(OMe)2)2}n (2), {[Cu(bpf)2(NO3)2]·PhtBu}n (3) and {[Cu(bpf)2(NO3)(H2O)]NO3·(bpf)0.5}n (4) were determined. The grid networks were held together by C–H···O and C–H···F hydrogen bonds via the NO3− anions and the tetrafluorophenylene rings of bpf, respectively. Biphenyl, m-dimethoxybenzene, t-butylbenzene, and bpf molecules were clathrated in cyclic cavities of the grid networks through arene-perfluoroarene interactions. These coordination networks have remarkable clathration ability for aromatic compounds.

Polymers, Vol. 3, Pages 1911-1933: Water-Soluble Stimuli Responsive Star-Shaped Segmented Macromolecules

Zacharoula Iatridi — Thu, 03 Nov 2011 00:00:00 CET

Star shaped segmented macromolecules constitute an interesting class of polymeric materials whose properties differ remarkably from those appearing in their linear counterparts. This review highlights the work done in the last decade, dealing with the self-assembly of star-shaped block copolymers and terpolymers of various topologies in aqueous media. This article focuses on a specific class of star shaped macromolecules designated as stimuli responsive. These stars bearblock/arms undergo sharp phase transitions upon responding to stimuli, such as temperature, pH, ionic strength and so forth. These transitions impose dramatic transformations on the morphology and, accordingly, in the functionality of the nanostructured associates. The number of arms, the specific functionality and topology of the different arm/blocks and the overall macromolecular architecture of the star polymer, significantly influence their behavior in terms of self-assembly and responsiveness.

Polymers, Vol. 3, Pages 1902-1910: Bacterial Inactivation Kinetics of Dialdehyde Starch Aqueous Suspension

Le Song — Thu, 03 Nov 2011 00:00:00 CET

The bacterial inactivation kinetics of dialdehyde starch (DAS) aqueous suspension was studied by the relationship between the minimal lethal concentration (MLC) and the inactivation time at four different temperatures. The relationship between MLC and exposure time was found to follow the first-order Chick-Watson law. This first-order inactivation kinetics was modeled by pseudo-first order chemical reaction. This model was validated by the successful predication of the bacterial inactivation response at room temperature.

Polymers, Vol. 3, Pages 1875-1901: Biomedical Activity of Chitin/Chitosan Based Materials—Influence of Physicochemical Properties Apart from Molecular Weight and Degree of N-Acetylation

Jolanta Kumirska — Thu, 03 Nov 2011 00:00:00 CET

The physicochemical nature of chitin and chitosan, which influences the biomedical activity of these compounds, is strongly related to the source of chitin and the conditions of the chitin/chitosan production process. Apart from widely described key factors such as weight-averaged molecular weight (MW) and degree of N-acetylation (DA), other physicochemical parameters like polydispersity (MW/MN), crystallinity or the pattern of acetylation (PA) have to be taken into consideration. From the biological point of view, these parameters affect a very important factor—the solubility of chitin and chitosan in water and organic solvents. The physicochemical properties of chitosan solutions can be controlled by manipulating solution conditions (temperature, pH, ionic strength, concentration, solvent). The degree of substitution of the hydroxyl and the amino groups or the degree of quaternization of the amino groups also influence the mechanical and biological properties of chitosan samples. Finally, a considerable research effort has been directed towards developing safe and efficient chitin/chitosan-based products because many factors, like the size of nanoparticles, can determine the biomedical characteristics of medicinal products. The influence of these factors on the biomedical activity of chitin/chitosan-based products is presented in this report in more detail.

Polymers, Vol. 3, Pages 1866-1874: One-Dimensional Helical Homochiral Metal-Organic Framework Built from 2,2′-Dihydroxy-1,1′-binaphthyl-3,3′-dicarboxylic Acid

Koichi Tanaka — Tue, 01 Nov 2011 00:00:00 CET

A homochiral metal-organic framework (MOF) based on enantiopure (R)-2,2′-dihydroxy-1,1′-binaphthyl-3,3′-dicarboxylic acid was synthesized. X-ray crystal diffraction studies revealed that the MOF adopts a one-dimensional infinite right-handed helical tubular structure along the a-axis, which serves as a host for the inclusion of guest dimethylformamide (DMF) molecules.

Polymers, Vol. 3, Pages 1849-1865: Preparation of Novel Hydrolyzing Urethane Modified Thiol-Ene Networks

Nicole M. Mackey — Tue, 25 Oct 2011 00:00:00 CEST

Novel tetra-functional hydrolyzing monomers were prepared from the reaction of TEOS and select alkene-containing alcohols, ethylene glycol vinyl ether or 2-allyloxy ethanol, and combined with trimethylolpropane tris(3-mercaptopropionate) (tri-thiol) in a thiol-ene “click” polymerization reaction to produce clear, colorless thiol-ene networks using both radiation and thermal-cure techniques. These networks were characterized for various mechanical characteristics, and found to posses Tg’s (DSC), hardness, tack, and thermal stability (TGA) consistent with their molecular structures. A new ene-modified urethane oligomer was prepared based on the aliphatic polyisocyanate Desmodur® N 3600 and added to the thiol-ene hydrolyzable network series in increasing amounts, creating a phase-segregated material having two Tg’s. An increase in water absorption in the ene-modified urethane formulations leading to a simultaneous increase in the rate of hydrolysis was supported by TGA data, film hardness measurements, and an NMR study of closely related networks. This phenomenon was attributed to the additional hydrogen bonding elements and polar functionality brought to the film with the addition of the urethane segment. SEM was utilized for visual analysis of topographical changes in the film’s surface upon hydrolysis and provides support for surface-driven erosion. Coatings prepared in this study are intended for use as hydrolyzing networks for marine coatings to protect against ship fouling.

Polymers, Vol. 3, Pages 1833-1848: Gold-Poly(methyl methacrylate) Nanocomposite Films for Plasmonic Biosensing Applications

Mohammed Alsawafta — Tue, 25 Oct 2011 00:00:00 CEST

Gold-poly(methyl methacrylate) nanocomposites are prepared by an in situ method, by irradiating spin-coated films containing the polymer and the gold precursor dissolved in acetone. The reduction of gold ions results in the formation of Au that nucleates and grows within the polymer film. It is shown that, depending on the energy source, gold nanoparticles with different shapes can be formed. Nanocomposites prepared through UV-, thermal-, and MW-irradiation, respectively, show a low sensitivity toward the environment. However, by annealing the samples at temperatures well above the glass transition temperature of the polymer, the response to dielectric environment appears to be enhanced significantly. The sensitivity of samples synthesized through the three different methods is found to be comparable, around 100 nm/RIU. The increased sensitivity of the annealed sample is accounted for by the increased mobility of both polymer chains and gold nanoparticles in the rubbery state of the material and the presence of the monomer. Gold nanoparticles “freed” from the strong interaction with the polymer are now able to feel the molecules from the surrounding environment. The results show that, by using adequate post-synthesis heat treatments, gold-polymer nanocomposites can be used as plasmonic sensing platforms.

Polymers, Vol. 3, Pages 1805-1832: Polymer and Water Dynamics in Poly(vinyl alcohol)/Poly(methacrylate) Networks. A Molecular Dynamics Simulation and Incoherent Neutron Scattering Investigation

Gaio Paradossi — Mon, 17 Oct 2011 00:00:00 CEST

Chemically cross-linked polymer networks of poly(vinyl alcohol)/poly(methacrylate) form monolitic hydrogels and microgels suitable for biomedical applications, such as in situ tissue replacement and drug delivery. In this work, molecular dynamics (MD) simulation and incoherent neutron scattering methods are used to study the local polymer dynamics and the polymer induced modification of water properties in poly(vinyl alcohol)/poly(methacrylate) hydrogels. This information is particularly relevant when the diffusion of metabolites and drugs is a requirement for the polymer microgel functionality. MD simulations of an atomic detailed model of the junction domain at the experimental hydration degree were carried out at 283, 293 and 313 K. The polymer-water interaction, the polymer connectivity and the water dynamics were investigated as a function of temperature. Simulation results are compared with findings of elastic and quasi-elastic incoherent neutron scattering measurements, experimental approaches which sample the same space-time window of MD simulations. This combined analysis shows a supercooled water component and an increase of hydrophilicity and mobility with temperature of these amphiphilic polymer networks.

Polymers, Vol. 3, Pages 1794-1804: Dependence of Optical and Microstructure Properties of Thiol-Capped Silver Nanoparticles Embedded in Polymeric Matrix

Angela Longo — Thu, 13 Oct 2011 00:00:00 CEST

Thiol-capped silver nanoparticles were prepared by in situ thermal decomposition of different silver(I)-thiolates precursors in a polymeric matrix. Depending on the structure of the organic coating, contact-free distribution of metal nanoparticles or nanoparticles aggregates were achieved. The structure and morphology of nanocomposites was analyzed by Transmission Electron Microscopy (TEM), and X-Ray Diffraction (XRD). Nanoparticles’ interaction was investigated by differential scanning calorimetry (DSC), and UV-Visible spectroscopy. In particular, only silver nanoparticles coated by n-alkyl thiols aggregated, while a contact-free dispersion was obtained by cyclohexyl thiol-capped silver nanoparticles.

Polymers, Vol. 3, Pages 1776-1793: Regeneration Approaches for Dental Pulp and Periapical Tissues with Growth Factors, Biomaterials, and Laser Irradiation

Chiaki Kitamura — Wed, 12 Oct 2011 00:00:00 CEST

In current dental practice, restorative and endodontic procedures have been developed in an attempt to preserve the vitality of dental pulp after exposure to external stimuli such as caries infection. When damage to dental pulp is reversible, pulp wound healing can proceed, whereas irreversible damage induces pathological changes in dental pulp, eventually requiring its removal. Furthermore, dentists sometimes extract non-vital teeth because of severe caries progression, critical size of periapical lesion, and tooth fracture. To overcome the limitations of presently available therapies, it is important to develop regeneration therapy for dental pulp and periapical tissues. In this review, we focus on the regeneration of dental pulp and periapical tissues by application of exogenous growth factors and scaffolds, as well as low-intensity laser irradiation as an auxiliary therapy for regeneration therapy.

Polymers, Vol. 3, Pages 1750-1775: Coordination Polymers and Metal Organic Frameworks Derived from 1,2,4-Triazole Amino Acid Linkers

Anil D. Naik — Tue, 11 Oct 2011 00:00:00 CEST

The perceptible appearance of biomolecules as prospective building blocks in the architecture of coordination polymers (CPs) and metal-organic frameworks (MOFs) are redolent of their inclusion in the synthon/tecton library of reticular chemistry. In this frame, for the first time a synthetic strategy has been established for amine derivatization in amino acids into 1,2,4-triazoles. A set of novel 1,2,4-triazole derivatized amino acids were introduced as superlative precursors in the design of 1D coordination polymers, 2D chiral helicates and 3D metal-organic frameworks. Applications associated with these compounds are diverse and include gas adsorption-porosity partitioning, soft sacrificial matrix for morphology and phase selective cadmium oxide synthesis, FeII spin crossover materials, zinc-b-lactamases inhibitors, logistics for generation of chiral/non-centrosymmetric networks; and thus led to a foundation of a new family of functional CPs and MOFs that are reviewed in this invited contribution.

Polymers, Vol. 3, Pages 1734-1749: Effect of Compatibilization on Poly-ε-Caprolactone Grafting onto Poly(ethylene-co-vinyl alcohol)

Samira Touhtouh — Tue, 11 Oct 2011 00:00:00 CEST

The non-miscibility of the reactants during solvent free poly-ε-caprolactone grafting onto poly(ethylene-co-vinyl alcohol) (EVOH) dramatically affects reaction kinetics. Different solutions were proposed to accelerate the exchange reactions between poly(ethylene-co-vinyl alcohol) and poly-ε-caprolactone. Reactions were conducted in a batch reactor or a mini twin-screw extruder. The addition of a poly(ethylene-co-vinyl alcohol)-g-poly-ε-caprolactone copolymer increased the compatibility of the reactants and led to a higher reaction rate. This copolymer was either prepared separately and added at the reaction beginning or prepared in situ grafting caprolactone from EVOH. The reactive system evolution was analyzed using molar mass evolution, microstructure characterization, thermal properties and the reactive blend morphology. The compatibilization effect combined with optimized reaction conditions, such as concentration and nature of catalyst and temperature, resulted in an important increase in reaction rates. Among the tested catalysts, 1,5,7-Triazabicyclo [4.4.0]dec-5-ene was a more efficient catalyst for grafting reactions than Tin (II) 2-ethylhexanoate.

Polymers, Vol. 3, Pages 1684-1733: Biodegradable Cell-Seeded Nanofiber Scaffolds for Neural Repair

Dong Han — Mon, 10 Oct 2011 00:00:00 CEST

Central and peripheral neural injuries are traumatic and can lead to loss of motor and sensory function, chronic pain, and permanent disability. Strategies that bridge the site of injury and allow axonal regeneration promise to have a large impact on restoring quality of life for these patients. Engineered materials can be used to guide axonal growth. Specifically, nanofiber structures can mimic the natural extracellular matrix, and aligned nanofibers have been shown to direct neurite outgrowth and support axon regeneration. In addition, cell-seeded scaffolds can assist in the remyelination of the regenerating axons. The electrospinning process allows control over fiber diameter, alignment, porosity, and morphology. Biodegradable polymers have been electrospun and their use in tissue engineering has been demonstrated. This paper discusses aspects of electrospun biodegradable nanofibers for neural regeneration, how fiber alignment affects cell alignment, and how cell-seeded scaffolds can increase the effectiveness of such implants.

Polymers, Vol. 3, Pages 1673-1683: Metal-Free Polymethyl Methacrylate (PMMA) Nanoparticles by Enamine “Click” Chemistry at Room Temperature

Lorea Buruaga — Fri, 07 Oct 2011 00:00:00 CEST

“Click” chemistry has become an efficient avenue to unimolecular polymeric nanoparticles through the self-crosslinking of individual polymer chains containing appropriate functional groups. Herein we report the synthesis of ultra-small (7 nm in size) polymethyl methacrylate (PMMA) nanoparticles (NPs) by the “metal-free” cross-linking of PMMA-precursor chains prepared by reversible addition-fragmentation chain transfer (RAFT) polymerization containing b-ketoester functional groups. Intramolecular collapse was performed by the one-pot reaction of b-ketoester moieties with alkyl diamines in tetrahydrofurane at r.t. (i.e., by enamine formation). The collapsing process was followed by size exclusion chromatography and by nuclear magnetic resonance spectroscopy. The size of the resulting PMMA-NPs was determined by dynamic light scattering. Enamine “click” chemistry increases the synthetic toolbox for the efficient synthesis of metal-free, ultra-small polymeric NPs.

Polymers, Vol. 3, Pages 1662-1672: Crystal Engineering: Synthesis and Structural Analysis of Coordination Polymers with Wavelike Properties

Omar W. Steward — Fri, 07 Oct 2011 00:00:00 CEST

Supramolecular coordination polymers with wavelike structures have been synthesized by self-assembly and their structures analyzed using the sine trigonometric function. Slow evaporation of a methylene chloride-methanol solution of a 1:1 molar mixture of [M(tmhd)2], where M = Co or Ni, and quinoxaline; a 1:2:1 molar mixture of [M(acac)2], where M = Co or Ni, 2,2,6,6-tetramethyl-3,5-heptadione and quinoxaline; or a 1:2:1 molar mixture of [Co(acac)2], dibenzoylmethane, and quinoxaline, yielded the crystalline coordination polymers. In the presence of the nitrogenous base, ligand scrambling occurs yielding the most insoluble product. The synthesis and structures of the following wavelike polymers are reported: trans-[Co(DBM)2(qox)]n·nH2O (2), trans-[Co(tmhd)2(qox)]n (3), trans-[Ni(tmhd)2(qox)]n (4), where DBM− = dibenzoylmethanate, tmhd− = 2,2,6,6-tetramethyl-3,5-heptadionate, and qox = quinoxaline. The wavelike structures are generated by intramolecular steric interactions and crystal packing forces between the chains. Some of the tert-butyl groups show a two-fold disorder. The sine function, φ = A sin 2πx/λ, where φ = distance (Ǻ) along the polymer backbone, λ = wavelength (Ǻ), A = amplitude (Ǻ), x = distance (Ǻ) along the polymer axis, provides a method to approximate and visualize the polymer structures.

Polymers, Vol. 3, Pages 1652-1661: Novel Countercation in MMX-Type Mixed-Valence Chain Compound: Coexistence of Neutral and Protonated Amino Substituents

Hiroaki Iguchi — Thu, 06 Oct 2011 00:00:00 CEST

The first MMX-type quasi-one-dimensional (Q1D) Pt chain complex (MMX chain) that contains a mono-protonated diamine as countercation, {o-(H3NC6H4NH2)}4[Pt2(pop)4I]·H2O (pop = P2H2O52–), was synthesized. According to the crystal structural analysis, –NH2 group was hydrogen-bonded to either lattice H2O molecule or –NH3+ group in addition to typical hydrogen bond between –NH3+ group and pop ligand. To control the partial deprotonation of the countercation will be an important method for achieving the high-conductive MMX-chain polymer by the hole doping.

Polymers, Vol. 3, Pages 1607-1651: Polysaccharides: The “Click” Chemistry Impact

Pierre-Henri Elchinger — Tue, 27 Sep 2011 00:00:00 CEST

Polysaccharides are complex but essential compounds utilized in many areas such as biomaterials, drug delivery, cosmetics, food chemistry or renewable energy. Modifications and functionalizations of such polymers are often necessary to achieve molecular structures of interest. In this area, the emergence of the “click” chemistry concept, and particularly the copper-catalyzed version of the Huisgen 1,3-dipolar cycloaddition reaction between terminal acetylenes and azides, had an impact on the polysaccharides chemistry. The present review summarizes the contribution of “click” chemistry in the world of polysaccharides.

Polymers, Vol. 3, Pages 1600-1606: Preparation and Characterization of Organic-Inorganic Hybrid Hydrogel Electrolyte Using Alkaline Solution

Masanobu Chiku — Mon, 26 Sep 2011 00:00:00 CEST

Organic-inorganic hybrid hydrogel electrolytes were prepared by mixing hydrotalcite, cross-linked potassium poly(acrylate) and 6 M KOH solution. The organic-inorganic hybrid hydrogel electrolytes had high ionic conductivity (0.456–0.540 S cm−1) at 30 °C. Moreover, the mechanical strength of the hydrogel electrolytes was high enough to form a 2–3 mm thick freestanding membrane because of the reinforcement with hydrotalcite.

Polymers, Vol. 3, Pages 1591-1599: Guiding Light in Electro-Optic Polymers

Anna L. Pyayt — Mon, 26 Sep 2011 00:00:00 CEST

Electro-optic polymers have unique photonic, electro-optic and mechanical properties that make them attractive to use in a wide range of devices starting from ultra-high bandwidth light modulators for optical communications to miniature low power components for on-chip optical interconnects. The main building blocks of those devices are optical waveguides, that due to versatility of the polymers can be fabricated as either traditional multi-layer polymer structures, silicon nano-slots filled with the polymer, or dynamically created waveguides based on field-induced guiding. In this paper we cover various types of waveguides and analyze their optimum designs depending on application.

Polymers, Vol. 3, Pages 1575-1590: The Effect of Co-Monomer Content on the Swelling/Shrinking and Mechanical Behaviour of Individually Adsorbed PNIPAM Microgel Particles

Anna Burmistrova — Mon, 26 Sep 2011 00:00:00 CEST

The swelling/deswelling behaviour of microgel particles in the bulk and at the surface was studied and correlated to their mechanical properties. We focused on two kinds of particles: pure PNIPAM and PNIPAM-co-AAc particles. It was shown that the two step volume phase transition found for PNIPAM-co-AAc particles in the bulk disappears after the adsorption at the surface and only a one step transition was identified. The transition temperature increased strongly with increasing the co-monomer content. The dependence of the Young’s modulus of the adsorbed microgel particles on the temperature and the co-monomer content was discussed. The investigations were performed via DLS and SFM.

Polymers, Vol. 3, Pages 1565-1574: Loading of Two Related Metal-Organic Frameworks (MOFs), [Cu2(bdc)2(dabco)] and [Cu2(ndc)2(dabco)], with Ferrocene

Romain Heck — Wed, 21 Sep 2011 00:00:00 CEST

We have studied the loading of two related, similar porous metal-organic frameworks (MOFs) [Cu2(bdc)2(dabco)] (1), and [Cu2(ndc)2(dabco)] (2) with ferrocene by exposing bulk powder samples to the corresponding vapor. On the basis of powder X-ray diffraction data and molecular dynamics (MD) calculations we propose that each pore can store one ferrocene molecule. Despite the rather pronounced similarity of the two MOFs a quite different behavior is observed, for 1 loading with ferrocene leads to an anisotropic 1% contraction, whereas for 2 no deformation is observed. Mössbauer spectroscopy studies reveal that the Fe oxidation level remains unchanged during the process. Time dependent studies reveal that the diffusion constant governing the loading from the gas-phase for 1 is approximately three times larger than the value for 2.

Polymers, Vol. 3, Pages 1554-1564: Polymeric Optical Code-Division Multiple-Access (CDMA) Encoder and Decoder Modules

Xuejun Lu — Mon, 19 Sep 2011 00:00:00 CEST

We propose a low cost polymeric optical waveguides-based optical CDMA encoder and decoder modules. The structures of the optical CDMA encoder and decoder modules are presented. The performance of the optical CDMA encoder and decoder modules is simulated using 10-chip binary phase-shift keying (BPSK) coding schemes. The optical CDMA encoder and decoder modules can effectively transmit and recover optical CDMA data streams. The SNR of the received signal is analyzed and determined to be primarily from the cross correlation with other channels.

Polymers, Vol. 3, Pages 1533-1553: NMR Studies and Molecular Dynamic Simulation of Synthetic Dendritic Antigens

Maria Isabel Montañez — Tue, 13 Sep 2011 00:00:00 CEST

A series of synthetic benzylpenicillinoylated dendrimers has been prepared using up to 4th generation PAMAM dendrimers. These nanoconjugates, as nanosized Dendritic Antigens, are useful in the diagnostic evaluation of drug allergy due to specific molecular recognition with the Human Immunological System (IgE). The morphology and dimensions of the conjugates coupled to the orientation of the peripheral benzylpenicillin residues in the dendrimers may play key roles in such molecular recognition processes. Herein, the characterization and conformation of these structures are studied by a detailed analysis of 1D (1H and 13C NMR) and 2D NMR (1H,1H-NOESY) spectra. These dendrimers in explicit solvent were studied by the atomistic forcefield-based molecular dynamics. Structural properties such as shape, radius-of-gyration and distribution of the monomers will be discussed in relation to the experimental observations.

Polymers, Vol. 3, Pages 1512-1532: Activity and Mechanism of Antimicrobial Peptide-Mimetic Amphiphilic Polymethacrylate Derivatives

Iva Sovadinova — Tue, 13 Sep 2011 00:00:00 CEST

Cationic amphiphilic polymethacrylate derivatives (PMAs) have shown potential as a novel class of synthetic antimicrobials. A panel of PMAs with varied ratios of hydrophobic and cationic side chains were synthesized and tested for antimicrobial activity and mechanism of action. The PMAs are shown to be active against a panel of pathogenic bacteria, including a drug-resistant Staphylococcus aureus, compared to the natural antimicrobial peptide magainin which did not display any activity against the same strain. The selected PMAs with 47–63% of methyl groups in the side chains showed minimum inhibitory concentrations of ≤2–31 µg/mL, but cause only minimal harm to human red blood cells. The PMAs also exhibit rapid bactericidal kinetics. Culturing Escherichia coli in the presence of the PMAs did not exhibit any potential to develop resistance against the PMAs. The antibacterial activities of PMAs against E. coli and S. aureus were slightly reduced in the presence of physiological salts. The activity of PMAs showed bactericidal effects against E. coli and S. aureus in both exponential and stationary growth phases. These results demonstrate that PMAs are a new antimicrobial platform with no observed development of resistance in bacteria. In addition, the PMAs permeabilized the E. coli outer membrane at polymer concentrations lower than their MIC values, but they did not show any effect on the bacterial inner membrane. This indicates that mechanisms other than membrane permeabilization may be the primary factors determining their antimicrobial activity.

Polymers, Vol. 3, Pages 1475-1511: An Excursion into the Intriguing World of Polymeric Tl(I) and Ag(I) Cyanoximates

Nikolay Gerasimchuk — Tue, 13 Sep 2011 00:00:00 CEST

The reaction of hot (~95 °C) aqueous solutions of Tl2CO3 with solid HL (HL = NC-C(=N-OH)-R is a cyanoxime, and R is an electron-withdrawing group; 37 ligands are known up-to-date) leads to crystalline yellow/orange TlL. Similarly, the reaction between AgNO3 and ML (M = K+, Na+; L = anion of the monodeprotonated cyanoxime) this time at room temperature in mixed ethanol/aqueous solutions leads to sparingly soluble, colored AgL in high-yield. All synthesized monovalent Tl and Ag complexes were characterized using a variety of spectroscopic methods and X-ray analysis, which revealed the formation of primarily 2D coordination polymers of different complexity. In all cases cyanoxime mono-anions act as bridging ligands. Thallium(I) cyanoximates adopt in most cases a double-stranded motif that is originated from centrosymmetric (TlL)2 dimers in which two Tl2O2 rhombs are fused into infinite “ladder-type” structure. There are very short (3.65–3.85 Å) intermetallic distances in (TlL)n, which are close to that (3.46 Å) in metallic thallium. This opens the possibility for the electrochemical or chemical generation of mixed valence Tl(I)/Tl(III) polymers that may exhibit electrical conductivity. Synthesized silver(I) compounds demonstrate a very significant (for multiple years!) stability towards visible light. There are three areas of potential practical applications of these unusual complexes: (1) battery-less detectors of UV-radiation, (2) non electrical sensors for gases of industrial importance, (3) antimicrobial additives to light-curable acrylate polymeric glues, fillers and adhesives used during introduction of indwelling medical devices. Chemical, structural, technological and biological aspects of application of Tl(I) and Ag(I) cyanoximes-based coordination polymers are reviewed.

Polymers, Vol. 3, Pages 1458-1474: A Molecular Antenna Coordination Polymer from Cadmium(II) and 4,4’-Bipyridine Featuring Three Distinct Polymer Strands in the Crystal

Rüdiger W. Seidel — Mon, 05 Sep 2011 00:00:00 CEST

Reaction of cadmium perchlorate and the prototypical linear bridging ligand 4,4’-bipyridine (4,4’-bipy) in an ethanol/water mixture affords the one-dimensional coordination polymer, [{Cd(m-4,4’-bipy)(4,4’-bipy)2(H2O)2}(ClO4)2 × 2 4,4’-bipy × 4.5 H2O]n (1). The Cd2+ ions adopt an octahedral coordination sphere and are joined into linear chains by 4,4’-bipy via two trans coordination sites. The remaining two trans sites in the equatorial plane carry terminally monodentate-bound 4,4’-bipy ligands, resulting in a molecular antenna arrangement. The two axial sites of each Cd2+ ion are occupied by aqua ligands. Compound 1 crystallizes in the non-centrosymmetric, monoclinic space group C2 with three similar, crystallographically independent, cationic coordination polymer strands in the unit cell, which essentially differ only in the conformations of the 4,4’-bipyridyl ligands. Consistent with the similarity of the local coordination environments of the three independent Cd atoms in the structure, 113Cd MAS NMR spectroscopy reveals a single resonance line at 89 ppm.

Polymers, Vol. 3, Pages 1447-1457: Photomechanical Response of Composite Structures Built from Azobenzene Liquid Crystal Polymer Networks

Kyung Min Lee — Fri, 02 Sep 2011 00:00:00 CEST

Optically directed shape adaptive responses have been sought after for many decades in photoresponsive polymeric materials. A number of recent examinations have elucidated elucidated the unique opportunities of photomechanical responses realized in azobenzene-functionalized liquid crystalline polymer networks (both elastomers and glasses). This work summarizes and contrasts the photomechanical response of glassy polydomain, monodomain, and twisted nematic azo-LCN materials to blue-green irradiation. Building from this summary, the combinatorial photomechanical response observed upon irradiation of composite cantilevers is examined. Large scale shape adaptations are realized, with novel responses that may be of potential use in future employment of these materials in actuation.

Polymers, Vol. 3, Pages 1433-1446: Microscopic and Spectroscopic Investigation of Poly(3-hexylthiophene) Interaction with Carbon Nanotubes

Michele Giulianini — Mon, 29 Aug 2011 00:00:00 CEST

The inclusion of carbon nanotubes in polymer matrix has been proposed to enhance the polymer’s physical and electrical properties. In this study, microscopic and spectroscopic techniques are used to investigate the interaction between poly(3-hexylthiophene) (P3HT) and nanotubes and the reciprocal modification of physical properties. The presence of P3HT-covered nanotubes dispersed in the polymer matrix has been observed by atomic force microscopy and transmission electron microscopy. Then, the modification of P3HT optical properties due to nanotube inclusion has been evidenced with spectroscopic techniques like absorption and Raman spectroscopy. The study is completed with detailed nanoscale analysis by scanning probe techniques. The ordered self assembly of polymer adhering on the nanotube is unveiled by showing an example of helical wrapping of P3HT. Scanning tunneling spectroscopy study provides information on the electronic structure of nanotube-polymer assembly, revealing the charge transfer from P3HT to the nanotube.

Polymers, Vol. 3, Pages 1423-1432: Consolidation of Inorganic Precipitated Silica Gel

Hussein Sahabi — Mon, 29 Aug 2011 00:00:00 CEST

Colloidal gels are possible intermediates in the generation of highly porous particle systems. In the production process the gels are fragmented after their formation. These gel fragments compact to particles whose application-technological properties are determined by their size and porosity. In the case of precipitated silica gels, this consolidation process depends on temperature and pH, among other parameters. It is shown that these dependencies can be characterized by oedometer measurements. Originally, the oedometer test (one-dimensional compression test) stemmed from soil mechanics. It has proven to be an interesting novel examination method for gels. Quantitative data of the time-dependent shrinkage of gel samples can be obtained. The consolidation of the gels shows a characteristic dependence on the above parameters.

Polymers, Vol. 3, Pages 1398-1422: Synthesis of Stimuli-responsive, Water-soluble Poly[2-(dimethylamino)ethyl methacrylate/styrene] Statistical Copolymers by Nitroxide Mediated Polymerization

Chi Zhang — Fri, 26 Aug 2011 00:00:00 CEST

2-(Dimethylamino)ethyl methacrylate/styrene statistical copolymers (poly(DMAEMA-stat-styrene)) with feed compositions fDMAEMA = 80–95 mol%, (number average molecular weights Mn = 9.5–11.2 kg mol−1) were synthesized using succinimidyl ester-functionalized BlocBuilder alkoxyamine initiator at 80 °C in bulk. Polymerization rate increased three-fold on increasing fDMAEMA = 80 to 95 mol%. Linear Mn increases with conversion were observed up to about 50% conversion and obtained copolymers possessed monomodal, relatively narrow molecular weight distributions (polydispersity = 1.32–1.59). Copolymers with fDMAEMA = 80 and 90 mol% were also cleanly chain-extended with DMAEMA/styrene mixtures of 95 and 90 mol% DMAEMA, respectively, confirming the livingness of the copolymers. Copolymer phase behavior in aqueous solutions was examined by dynamic light scattering and UV-Vis spectroscopy. All copolymers exhibited lower critical solution temperature (LCST)-type behavior. LCST decreased with increasing styrene content in the copolymer and with increasing solution concentration. All copolymers were completely water-soluble and temperature insensitive at pH 4 but were more hydrophobic at pH 10, particularly copolymers with fDMAEMA = 80 and 85 mol%, which were water-insoluble. At pH 10, LCST of copolymers with fDMAEMA = 90 and 95 mol% were more than 10 °C lower compared to their solutions in neutral, de-ionized water. Block copolymers with two statistical blocks with different DMAEMA compositions exhibited a single LCST, suggesting the block segments were not distinct enough to exhibit separate LCSTs in water.

Polymers, Vol. 3, Pages 1377-1397: Poly Lactic-co-Glycolic Acid (PLGA) as Biodegradable Controlled Drug Delivery Carrier

Hirenkumar K. Makadia — Fri, 26 Aug 2011 00:00:00 CEST

In past two decades poly lactic-co-glycolic acid (PLGA) has been among the most attractive polymeric candidates used to fabricate devices for drug delivery and tissue engineering applications. PLGA is biocompatible and biodegradable, exhibits a wide range of erosion times, has tunable mechanical properties and most importantly, is a FDA approved polymer. In particular, PLGA has been extensively studied for the development of devices for controlled delivery of small molecule drugs, proteins and other macromolecules in commercial use and in research. This manuscript describes the various fabrication techniques for these devices and the factors affecting their degradation and drug release.

Polymers, Vol. 3, Pages 1363-1376: Influence of the Hydrophobicity of Polyelectrolytes on Polyelectrolyte Complex Formation and Complex Particle Structure and Shape

Mandy Mende — Thu, 25 Aug 2011 00:00:00 CEST

Polyelectrolyte complexes (PECs) were prepared by structural uniform and strongly charged cationic and anionic modified alternating maleic anhydride copolymers. The hydrophobicity of the polyelectrolytes was changed by the comonomers (ethylene, isobutylene and styrene). Additionally, the n−/n+ ratio of the molar charges of the polyelectrolytes and the procedure of formation were varied. The colloidal stability of the systems and the size, shape, and structure of the PEC particles were investigated by turbidimetry, dynamic light scattering (DLS) and atomic force microscopy (AFM). Dynamic light scattering indicates that beside large PEC particle aggregates distinct smaller particles were formed by the copolymers which have the highest hydrophobicity (styrene). These findings could be proved by AFM. Fractal dimension (D), root mean square (RMS) roughness and the surface profiles of the PEC particles adsorbed on mica allow the following conclusions: the higher the hydrophobicity of the polyelectrolytes, the broader is the particle size distribution and the minor is the swelling of the PEC particles. Hence, the most compact particles are formed with the very hydrophobic copolymer.

Polymers, Vol. 3, Pages 1352-1362: Nanocomposites Based on Metal and Metal Sulfide Clusters Embedded in Polystyrene

Gianfranco Carotenuto — Mon, 22 Aug 2011 00:00:00 CEST

Transition-metal alkane-thiolates (i.e., organic salts with formula Me(SR)x, where R is a linear aliphatic hydrocarbon group, –CnH2n+1) undergo a thermolysis reaction at moderately low temperatures (close to 200 °C), which produces metal atoms or metal sulfide species and an organic by-product, disulfide (RSSR) or thioether (RSR) molecules, respectively. Alkane-thiolates are non-polar chemical compounds that dissolve in most techno-polymers and the resulting solid solutions can be annealed to generate polymer-embedded metal or metal sulfide clusters. Here, the preparation of silver and gold clusters embedded into amorphous polystyrene by thermolysis of a dodecyl-thiolate precursor is described in detail. However, this chemical approach is quite universal and a large variety of polymer-embedded metals or metal sulfides could be similarly prepared.

Polymers, Vol. 3, Pages 1325-1351: Theory-Guided Design of Organic Electro-Optic Materials and Devices

Larry Dalton — Fri, 19 Aug 2011 00:00:00 CEST

Integrated (multi-scale) quantum and statistical mechanical theoretical methods have guided the nano-engineering of controlled intermolecular electrostatic interactions for the dramatic improvement of acentric order and thus electro-optic activity of melt-processable organic polymer and dendrimer electro-optic materials. New measurement techniques have permitted quantitative determination of the molecular order parameters, lattice dimensionality, and nanoscale viscoelasticity properties of these new soft matter materials and have facilitated comparison of theoretically-predicted structures and thermodynamic properties with experimentally-defined structures and properties. New processing protocols have permitted further enhancement of material properties and have facilitated the fabrication of complex device structures. The integration of organic electro-optic materials into silicon photonic, plasmonic, and metamaterial device architectures has led to impressive new performance metrics for a variety of technological applications.

Polymers, Vol. 3, Pages 1310-1324: Simplified Reflection Fabry-Perot Method for Determination of Electro-Optic Coefficients of Poled Polymer Thin Films

Dong Hun Park — Thu, 18 Aug 2011 00:00:00 CEST

We report a simplified reflection mode Fabry-Perot interferometry method for determination of electro-optic (EO) coefficients of poled polymer thin films. Rather than fitting the detailed shape of the Fabry-Perot resonance curve, our simplification involves a technique to experimentally determine the voltage-induced shift in the angular position of the resonance minimum. Rigorous analysis based on optical properties of individual layers of the multilayer structure is not necessary in the data analysis. Although angle scans are involved, the experimental setup does not require a θ-2θ rotation stage and the simplified analysis is an advantage for polymer synthetic efforts requiring quick and reliable screening of new materials. Numerical and experimental results show that our proposed method can determine EO coefficients to within an error of ~8% if poled values for the refractive indices are used.

Polymers, Vol. 3, Pages 1297-1309: Investigation of Second-Harmonic Generation and Molecular Orientation in Electrostatically Self-Assembled Thin Films

Liangmin Zhang — Thu, 18 Aug 2011 00:00:00 CEST

We report the observation and measurement of second-harmonic generation in self-assembled ultra thin film nonlinear optical materials using a femtosecond high repetition rate laser system. Second-harmonic intensity, as a function of the incident angle in these films, has been measured using incident p-polarized and s-polarized optical beam components. The second-order nonlinear optical susceptibilities of the thin films have also been determined. Using a curve fitting method and a crystal reference material, we have obtained second-order susceptibilities c333 = 6.17 ± 0.18 pm/V and c311 = 0.68 ± 0.02 pm/V at a fundamental wavelength of 1,200 nm. Based on linear molecular model approximation, we have also used the fitted data to investigate the average orientation distribution of the chromophore dipoles in the self-assembled film. The result indicates that the average tilt angle of the chromophore dipoles away from the substrate normal line is 25.2° ± 0.8°.

Polymers, Vol. 3, Pages 1282-1296: Activity and Export of Engineered Nisin-(1-22) Analogs

Annechien Plat — Fri, 12 Aug 2011 00:00:00 CEST

The pentacyclic peptide antibiotic nisin, produced by Lactococcus lactis is ubiquitously applied as a food preservative. We previously demonstrated that the truncated nisin-(1-22) has only 10-fold lower activity than nisin. Here we aimed at further developing this tricyclic nisin analog to reach activity comparable to that of nisin. Our data demonstrate that: (1) ring A has a large mutational freedom; (2) the composition of residues 20–22 strongly affects production levels of nisin-(1-22); (3) a positively charged C-terminus of nisin-(1-22) significantly enhances its antimicrobial activity; (4) nisin-(1-22) inhibits in vitro growth of a target strain using different dynamics than nisin.

Polymers, Vol. 3, Pages 1268-1281: Defensins: Potential Effectors in Autoimmune Rheumatic Disorders

Stefan Vordenbäumen — Thu, 11 Aug 2011 00:00:00 CEST

Defensins are small cationic peptides with antimicrobial properties. They constitute a highly conserved innate immune defense mechanism across species. Based on the arrangement of disulfide-bonds, α- and β-defensins are distinguished in humans. Both types of defensin comprise several distinct molecules that are preferentially expressed at epithelial surfaces and in blood cells. In the last decade, multiple immunomodulatory functions of defensins have been recognized, including chemotactic activity, the promotion of antigen presentation, and modulations of proinflammatory cytokine secretion. These findings suggested a role for defensins not only as a first line of defense, but also as connectors of innate and adaptive immune responses. Recently, increasingly accumulating evidence has indicated that defensins may also be involved in the pathogenesis of autoimmune rheumatic disorders such as systemic lupus erythematosus and rheumatoid arthritis. The current review summarizes the data connecting defensins to autoimmunity.

Polymers, Vol. 3, Pages 1255-1267: Spontaneous Vesicles Modulated by Polymers

M. Mercedes Velázquez — Mon, 08 Aug 2011 00:00:00 CEST

Vesicles are widely used in technological applications including cosmetic products, in microencapsulation for drug delivery, as anticancer agents and in the technology of adhesives, paints and inks. The vesicle size and the surface charge are very important properties from a technological point of view. Thus, the challenge in formulation is to find inexpensive stable vesicles with well-defined sizes and to modulate the surface charge of these aggregates. In this work we analyze the effect of different polymers on the structural properties of vesicles of the biodegradable surfactant sodium bis(2-ethyl-hexyl) sulfosuccinate, Aerosol OT. Using fluorescence, conductivity, electrophoretic mobility and dynamic light scattering measurements we study the effect of the polymer nature, molecular weight and polymer concentration on the stability and the vesicle size properties. Results demonstrate that it is possible to modulate both the size and the electric surface charge of spontaneous vesicles of Aerosol OT by the addition of very small percentages of poly(allylamine) and poly(maleic anhydride-alt-1-octadecen).

Polymers, Vol. 3, Pages 1243-1254: Evaluation of the Biological Effects of Externally Tunable, Hydrogel Encapsulated Quantum Dot Nanospheres in Escherichia coli

Somesree GhoshMitra — Mon, 08 Aug 2011 00:00:00 CEST

Quantum Dots (QDs) have become an interesting subject of study for labeling and drug delivery in biomedical research due to their unique responses to external stimuli. In this paper, the biological effects of a novel hydrogel based QD nano-structure on E. coli bacteria are presented. The experimental evidence reveals that cadmium telluride (CdTe) QDs that are encapsulated inside biocompatible polymeric shells have reduced or negligible toxicity to this model cell system, even when exposed at higher dosages. Furthermore, a preliminary gene expression study indicates that QD-hydrogel nanospheres do not inhibit the Green Fluorescent Protein (GFP) gene expression. As the biocompatible and externally tunable polymer shells possess the capability to control the QD packing density at nanometer scales, the resulting luminescence efficiency of the nanostructures, besides reducing the cytotoxic potential, may be suitable for various biomedical applications.

Polymers, Vol. 3, Pages 1215-1242: Thermoresponsive Polymers for Biomedical Applications

Mark A. Ward — Wed, 03 Aug 2011 00:00:00 CEST

Thermoresponsive polymers are a class of “smart” materials that have the ability to respond to a change in temperature; a property that makes them useful materials in a wide range of applications and consequently attracts much scientific interest. This review focuses mainly on the studies published over the last 10 years on the synthesis and use of thermoresponsive polymers for biomedical applications including drug delivery, tissue engineering and gene delivery. A summary of the main applications is given following the different studies on thermoresponsive polymers which are categorized based on their 3-dimensional structure; hydrogels, interpenetrating networks, micelles, crosslinked micelles, polymersomes, films and particles.

Polymers, Vol. 3, Pages 1199-1214: Dark Antimicrobial Mechanisms of Cationic Phenylene Ethynylene Polymers and Oligomers against Escherichia coli

Ying Wang — Fri, 29 Jul 2011 00:00:00 CEST

The interactions of poly(phenylene ethynylene) (PPE)-based cationic conjugated polyelectrolytes (CPEs) and oligo-phenylene ethynylenes (OPEs) with E. coli cells are investigated to gain insights into the differences in the dark killing mechanisms between CPEs and OPEs. A laboratory strain of E. coli with antibiotic resistance is included in this work to study the influence of antibiotic resistance on the antimicrobial activity of the CPEs and OPEs. In agreement with our previous findings, these compounds can efficiently perturb the bacterial cell wall and cytoplasmic membrane, resulting in bacterial cell death. Electron microscopy imaging and cytoplasmic membrane permeability assays reveal that the oligomeric OPEs penetrate the bacterial outer membrane and interact efficiently with the bacterial cytoplasmic membrane. In contrast, the polymeric CPEs cause serious damage to the cell surface. In addition, the minimum inhibitory concentration (MIC) and hemolytic concentration (HC) of the CPEs and OPEs are also measured to compare their antimicrobial activities against two different strains of E. coli with the compounds’ toxicity levels against human red blood cells (RBC). MIC and HC measurements are in good agreement with our previous model membrane perturbation study, which reveals that the different membrane perturbation abilities of the CPEs and OPEs are in part responsible for their selectivity towards bacteria compared to mammalian cells. Our study gives insight to several structural features of the PPE-based CPEs and OPEs that modulate their antimicrobial properties and that these features can serve as a basis for further tuning their structures to optimize antimicrobial properties.

Polymers, Vol. 3, Pages 1181-1198: Microspheres Containing Cibacron Blue F3G-A and Incorporated Iron Oxide Nanoparticles as Biomarker Harvesting Platforms

Alexis Patanarut — Thu, 28 Jul 2011 00:00:00 CEST

In this work, magnetic functionality was introduced to cross-linked acrylamide-based particles via the in situ coprecipitation of iron oxide nanoparticles within the hydrogel particle interior. Cibacron Blue F3G-A was then incorporated onto the magnetic hydrogel scaffold to facilitate the harvest of targeted protein species. The dye-loaded magnetic particles were physically characterized, and their protein sequestration performance was investigated. The results of these studies indicated that dye-loaded magnetic particles sequestered a greater amount of lower molecular weight proteins from the test solution than was achieved using reference particles, dye-loaded cross-linked N-isopropylacrylamide-based core-shell particles. This difference in protein harvesting ability may reflect the higher degree of dye-loading in the magnetic particles relative to the dye-loaded core-shell particles.

Polymers, Vol. 3, Pages 1162-1180: Polymer-Optical-Fiber Lasers and Amplifiers Doped with Organic Dyes

Jon Arrue — Mon, 25 Jul 2011 00:00:00 CEST

Polymer optical fibers (POFs) doped with organic dyes can be used to make efficient lasers and amplifiers due to the high gains achievable in short distances. This paper analyzes the peculiarities of light amplification in POFs through some experimental data and a computational model capable of carrying out both power and spectral analyses. We investigate the emission spectral shifts and widths and on the optimum signal wavelength and pump power as functions of the fiber length, the fiber numerical aperture and the radial distribution of the dopant. Analyses for both step-index and graded-index POFs have been done.

Polymers, Vol. 3, Pages 1151-1161: Tunable Crystal-to-Crystal Phase Transition in a Cadmium Halide Chain Polymer

Kevin Lamberts — Mon, 25 Jul 2011 00:00:00 CEST

The chain polymer [{Cd(μ-X)2py2}1∞] (X = Cl, Br; py = pyridine) undergoes a fully reversible phase transition between a monoclinic low-temperature and an orthorhombic high-temperature phase. The transformation can be directly monitored in single crystals and can be confirmed for the bulk by powder diffraction. The transition temperature can be adjusted by tuning the composition of the mixed-halide phase: Transition temperatures between 175 K up to the decomposition of the material at ca. 350 K are accessible. Elemental analysis, ion chromatography and site occupancy refinements from single-crystal X-ray diffraction agree with respect to the stoichiometric composition of the samples.

Polymers, Vol. 3, Pages 1126-1150: Towards Extrusion of Ionomers to Process Fuel Cell Membranes

Yannick Molmeret — Tue, 19 Jul 2011 00:00:00 CEST

While Proton Exchange Membrane Fuel Cell (PEMFC) membranes are currently prepared by film casting, this paper demonstrates the feasibility of extrusion, a solvent-free alternative process. Thanks to water-soluble process-aid plasticizers, duly selected, it was possible to extrude acidic and alkaline polysulfone ionomers. Additionally, the feasibility to extrude composites was demonstrated. The impact of the plasticizers on the melt viscosity was investigated. Following the extrusion, the plasticizers were fully removed in water. The extrusion was found to impact neither on the ionomer chains, nor on the performances of the membrane. This environmentally friendly process was successfully validated for a variety of high performance ionomers.

Polymers, Vol. 3, Pages 1107-1125: In Vitro and In Vivo Evaluation of a Folate-Targeted Copolymeric Submicrohydrogel Based on N-Isopropylacrylamide as 5-Fluorouracil Delivery System

M. Dolores Blanco — Mon, 18 Jul 2011 00:00:00 CEST

Folate-targeted poly[(p-nitrophenyl acrylate)-co-(N-isopropylacrylamide)] nanohydrogel (F-SubMG) was loaded with 5-fluorouracil (5-FU) to obtain low (16.3 ± 1.9 μg 5-FU/mg F-SubMG) and high (46.8 ± 3.8 μg 5-FU/mg F-SubMG) load 5-FU-loaded F-SubMGs. The complete in vitro drug release took place in 8 h. The cytotoxicity of unloaded F-SubMGs in MCF7 and HeLa cells was low; although it increased for high F-SubMG concentration. The administration of 10 μM 5-FU by 5-FU-loaded F-SubMGs was effective on both cellular types. Cell uptake of F-SubMGs took place in both cell types, but it was higher in HeLa cells because they are folate receptor positive. After subcutaneous administration (28 mg 5-FU/kg b.w.) in Wistar rats, F-SubMGs were detected at the site of injection under the skin. Histological studies indicated that the F-SubMGs were surrounded by connective tissue, without any signs of rejections, even 60 days after injection. Pharmacokinetic study showed an increase in MRT (mean residence time) of 5-FU when the drug was administered by drug-loaded F-SubMGs.

Polymers, Vol. 3, Pages 1091-1106: Mechanical Properties and Adhesion of a Micro Structured Polymer Blend

Brunero Cappella — Fri, 15 Jul 2011 00:00:00 CEST

A 50:50 blend of polystyrene (PS) and poly(n-butyl methacrylate) (PnBMA) has been characterized with an Atomic Force Microscope (AFM) in Tapping Mode and with force-distance curves. The polymer solution has been spin-coated on a glass slide. PnBMA builds a uniform film on the glass substrate with a thickness of @200 nm. On top of it, the PS builds an approximately 100 nm thick film. The PS-film undergoes dewetting, leading to the formation of holes surrounded by about 2 µm large rims. In those regions of the sample, where the distance between the holes is larger than about 4 µm, light depressions in the PS film can be observed. Topography, dissipated energy, adhesion, stiffness and elastic modulus have been measured on these three regions (PnBMA, PS in the rims and PS in the depressions). The two polymers can be distinguished in all images, since PnBMA has a higher adhesion and a smaller stiffness than PS, and hence a higher dissipated energy. Moreover, the polystyrene in the depressions shows a very high adhesion (approximately as high as PnBMA) and its stiffness is intermediate between that of PnBMA and that of PS in the rims. This is attributed to higher mobility of the PS chains in the depressions, which are precursors of new holes.

Polymers, Vol. 3, Pages 1076-1090: Multimeric, Multifunctional Derivatives of Poly(ethylene glycol)

Marina Zacchigna — Wed, 13 Jul 2011 00:00:00 CEST

This article reviews the use of multifunctional polymers founded on high-molecular weight poly(ethylene glycol) (PEG). The design of new PEG derivatives assembled in a dendrimer-like multimeric fashion or bearing different functionalities on the same molecule is described. Their use as new drug delivery systems based on the conjugation of multiple copies or diversely active drugs on the same biocompatible support is illustrated.

Polymers, Vol. 3, Pages 1065-1075: Thermal Cloud Point Fractionation of Poly(vinyl alcohol-co-vinyl acetate): Partition of Nanogels in the Fractions

Leonard I. Atanase — Mon, 04 Jul 2011 00:00:00 CEST

Poly(vinyl acetate-co-vinyl alcohol) (PVA), well-known as emulsion stabilizers, are obtained by partial hydrolysis of poly(vinyl acetate) (PVAc). Their thermal cloud point fractionation was performed in aqueous medium between 40 and 75 °C. This fractionation was carried out in order to get an insight in the partition of the initially present nanogels in the different fractions. All the fractions were characterized by size exclusion chromatography (SEC), NMR and dynamic light scattering (DLS) giving access to average degree of polymerization , DPw average degree of hydrolysis DH, average sequence lengths of vinyl acetate VAc, volume fraction and average size diameter (Dv) of nanogels and “free PVA chains”. The polydispersity of the samples in DPw, DH and VAc could be confirmed. The nanogels characterized by the highest values of volume fraction and Dv, in the range of 40–43 nm, were separated in the first coacervate fraction, whereas the most soluble fraction with low VAc content does not contain nanogels but only “free chains” of a Dv value of around 7–8 nm. The nanogels in the various fractions could further be disaggregated into “free chains” by complex formation with sodium dodecyl sulfate (SDS).

Polymers, Vol. 3, Pages 1051-1064: Synthesis of Diblock Copolymer Consisting of Poly(4-butyltriphenylamine) and Morphological Control in Photovoltaic Application

Kousuke Tsuchiya — Fri, 01 Jul 2011 00:00:00 CEST

The diblock copolymer PTPA-b-PS consisting of poly(4-butyltripheneylamine) (PTPA) and polystyrene was prepared by atom transfer radical polymerization followed by C–N coupling polymerization. Three types of block copolymers with different contents of polystyrene segment were prepared. The formation of block copolymer was confirmed by 1H NMR spectra and gel permeation chromatography (GPC) profiles. Time of flight (TOF) measurement revealed that the block copolymer showed higher hole mobility up to 1.3 × 10−4 cm2/Vs compared with PTPA homopolymer. The surface morphology of block copolymer films blended with [6,6]-phenyl-C61-butyric acid methyl ester (PCBM) was investigated by Atomic force microscopy (AFM). Introduction of polystyrene segment provided microphase-separated structures with domain sizes of around 20 nm. The photovoltaic device based on PTPA-b-PS, PTPA, and PCBM exhibited higher efficiency than that of homopolymer blend system.

Polymers, Vol. 3, Pages 1036-1050: Stimulus-Responsive Heteroaggregation of Colloidal Dispersions: Reversible Systems and Composite Materials

Melanie Bradley — Fri, 01 Jul 2011 00:00:00 CEST

Heteroaggregation is the aggregation of mixed particle systems where the colloidal particles may differ in charge, size and chemical composition. The phenomenon of heteroaggregation is of great relevance in industrial processes and the natural environment. This review will focus on binary heteroaggregation where at least one of the particles is a stimulus-responsive smart particle. Aggregation under various conditions of pH, temperature, light and relative concentration can be induced by the careful manipulation of any one or more of these environmental conditions during the heteroaggregation of smart particles. Stimulus response provides the potential for reversibility from an aggregated to a stable system and exceptional control over inter-particle interactions. The significant fundamental and applied studies that have made an impact in this area will be discussed.

Polymers, Vol. 3, Pages 1029-1035: Observation of Long-Range Vicinal Effect in Chiral Cu(II)-Cr(VI) or Cu(II)-W(VI) Bimetallic Coordination Polymers

Naoshi Hayashi — Wed, 29 Jun 2011 00:00:00 CEST

We have prepared some diastereomers of [CuL2][M2O7] (L is 1,2-diaminocyclohexane and its derivatives; M = Cr and W) bimetallic coordination polymers and confirmed their structural similarity and inner electronic states by means of XRD and XAS, respectively. For the first time, we have successfully observed distant vicinal effect of which the chiral source is only chiral organic ligands of [CuL2]2+ moieties (acting as ligand complex), while probe bands for solid state CD spectra are charge transfer (CT) bands of [M2O7]2− moieties (achiral complex) with the d0 electronic configuration. The new concept (interpretation) of this observation will be important for supramolecular chirality of coordination polymers built by ligand complexes.

Polymers, Vol. 3, Pages 1006-1028: Exploit the Bandwidth Capacities of the Perfluorinated Graded Index Polymer Optical Fiber for Multi-Services Distribution

Christophe Lethien — Wed, 29 Jun 2011 00:00:00 CEST

The study reported here deals with the exploitation of perfluorinated graded index polymer optical fiber bandwidth to add further services in a home/office network. The fiber properties are exhibited in order to check if perfluorinated graded index plastic optical fiber (PFGI-POF) is suitable to support a multiplexing transmission. According to the high bandwidth length of plastic fibers, both at 850 nm and 1,300 nm, the extension of the classical baseband existing network is proposed to achieve a dual concept, allowing the indoor coverage of wireless signals transmitted using the Radio over Fiber technology. The simultaneous transmission of a 10 GbE signal and a wireless signal is done respectively at 850 nm and 1,300 nm on a single plastic fiber using wavelength division multiplexing commercially available devices. The penalties have been evaluated both in digital (Bit Error Rate measurement) and radiofrequency (Error Vector Magnitude measurement) domains.

Polymers, Vol. 3, Pages 998-1005: The Effects of Exposure Time on the Surface Microhardness of Three Dual-Cured Dental Resin Cements

Tatiana C. Aguiar — Tue, 28 Jun 2011 00:00:00 CEST

This study evaluated the exposure time of light-curing of the polymers used for cementation on microhardness test in different storage times. The polymers (specifically called resin cements) were RelyX ARC, RelyX U100, and SET. Five specimens of each group were prepared and photo-polymerized with exposure times of 20 s and 180 s, using a LED polymerization unit with wavelength of 440 ~ 480 nm and light output was consistently 1,500 mW/cm2. The Vickers hardness test was performed in a MMT-3 Microhardness Tester. Data were submitted to ANOVA and Tukey's test (α = 0.05). The values of RelyX ARC showed statistically significant difference to groups with light exposure when considering only chemical cure (p < 0.05). The groups with light exposure (20 s and 180 s) showed no significant difference between them (p > 0.05). The RelyX U100 cured only chemically showed statistically significant difference between 48 h and 7 days (p < 0.05). The SET resin cement showed no significant difference to groups without light exposure for all storage times (p > 0.05). The values of hardening of the dual-cured resin cements improved after setting by light and chemical activation demonstrating the importance of light curing.

Polymers, Vol. 3, Pages 975-997: Integrated Photonic Devices Incorporating Low-Loss Fluorinated Polymer Materials

Min-Cheol Oh — Fri, 24 Jun 2011 00:00:00 CEST

Low-loss polymer materials incorporating fluorinated compounds have been utilized for the investigation of various functional optical devices useful for optical communication and optical sensor systems. Since reliability issues concerning the polymer device have been resolved, polymeric waveguide devices have been gradually adopted for commercial application systems. The two most successfully commercialized polymeric integrated optic devices, variable optical attenuators and digital optical switches, are reviewed in this paper. Utilizing unique properties of optical polymers which are not available in other optical materials, novel polymeric optical devices are proposed including widely tunable external cavity lasers and integrated optical current sensors.

Polymers, Vol. 3, Pages 967-974: A Novel Self-Assembled Liposome-Based Polymeric Hydrogel for Cranio-Maxillofacial Applications: Preliminary Findings

Victor Joo — Tue, 14 Jun 2011 00:00:00 CEST

Soft nanogels are submicron-sized hydrophilic structures engineered from biocompatible polymers possessing the characteristics of nanoparticles as well as hydrogels, with a wide array of potential applications in biotechnology and biomedicine, namely, drug and protein delivery. In this work, nanogels were obtained using the physical self-assembly technique or ‘layer-by-layer’ which is based on electrostatic interactions. Liposomal vesicles were coated with alternating layers of hyaluronic acid and chitosan yielding a more viscous hydrogel formulation that previously reported core-shell nanoparticulate suspension, via simply modifying the physico-chemical characteristics of the system. Structural features, size, surface charge, stability and swelling characteristics of the nanogel were studied using scanning electron microscopy and dynamic light scattering. With a specific cranio-maxillofacial application in mind, the hydrogel was loaded with recombinant human (rh) bone morphogenetic protein-7, also known as osteogenic protein-1 or rhOP-1 and release was monitored over an extended period of 60 days. This preliminary study reports promising results on the formulation of a novel core-shell polymeric nanogel.

Polymers, Vol. 3, Pages 955-966: Effect of Moisture on the Orientation Birefringence of Cellulose Esters

Mohd Edeerozey Abd Manaf — Tue, 14 Jun 2011 00:00:00 CEST

Orientation birefringence and its wavelength dispersion are studied for hot-drawn films of cellulose esters such as cellulose triacetate (CTA), cellulose diacetate (CDA), and cellulose acetate propionate (CAP) exposed to three different humidities of environments. Hot-drawn CTA films show negative birefringence that decreases with increasing wavelength. On the other hand, CDA and CAP films show positive birefringence that increases with increasing wavelength, i.e., the so-called extraordinary wavelength dispersion of birefringence. Upon exposure to high humidity environment, the orientation birefringence of CDA and CAP decreases. The decrease is prominent for the samples containing a large amount of water. CTA, however, shows an increase in magnitude of its negative orientation birefringence with increasing moisture content. The results can be explained by the increase of the polarizability anisotropy perpendicular to the stretching direction in the cellulose esters. It is found from ATR-FTIR measurements that hydrogen bonds are formed between carbonyl groups of cellulose esters and water molecules. Considering that orientation birefringence of cellulose esters is determined mainly by ester groups, the formation of hydrogen bonds contributes to the polarizability anisotropy, thus affecting the orientation birefringence.

Polymers, Vol. 3, Pages 942-954: Behavior of Na+-Polystyrene Sulfonate at the Interface with Single-Walled Carbon Nanotubes (SWNTs) and Its Implication to SWNT Suspension Stability

Tabbetha Dobbins — Tue, 14 Jun 2011 00:00:00 CEST

The assembly of sodium polystyrene sulfonate (Na+-PSS) at the surface of single-walled carbon nanotubes (SWNTs) in pH 3 aqueous solution is described. Rather than forming linear or sheet-like chain morphologies over SWNT surfaces, Na+-PSS adopts a spherically collapsed conformation believed to be the result of cation (either Na+ or H+) condensation onto the ionized polymer chain. It is well reported that cations (and also anions) adsorb preferentially onto single-walled and multi-walled carbon nanotube surfaces leading to an increased ion concentration in the near surface regions relative to the bulk solution. This work provides experimental evidence for preferentially absorbed cation condensation onto PSS anions until those cations are spaced at distances corresponding to the Bjerrum length ( B), as defined by the Manning theory of ion condensation, at the SWNT surface. The resulting electrostearic repulsions allow the SWNTs to remain suspended for days. Furthermore , coulombic repulsion among SWNT bundles after cation adsorption alone is not sufficient to form stable suspensions—but rather the stearic repulsions associated with spherically collapsed PSS at the nanotube surface is responsible for suspension stability. It is believed that the ultrasonic agitation drives cations into the small spaces between SWNT bundles and coulombic potential attracts the PSS to those regions.

Polymers, Vol. 3, Pages 928-941: Physical and Chemical Characterization of Poly(hexamethylene biguanide) Hydrochloride

Gustavo F. De Paula — Wed, 01 Jun 2011 00:00:00 CEST

We present the characterization of commercially available Poly(hexamethylene biguanide) hydrochloride (PHMB), a polymer with biocidal activity and several interesting properties that make this material suitable as a building block for supramolecular chemistry and “smart” materials. We studied polymer structure in water solution by dynamic light scattering, surface tension and capacitance spectroscopy. It shows typical surfactant behavior due to amphiphilic structure and low molecular weight. Spectroscopic (UV/Vis, FT-NIR) and thermal characterization (differential scanning calorimetry, DSC, and thermogravimetric analysis, TGA) were performed to give additional insight into the material structure in solution and solid state. These results can be the foundation for more detailed investigations on usefulness of PHMB in new complex materials and devices.

Polymers, Vol. 3, Pages 915-927: Using Light Scattering to Screen Polyelectrolytes (PEL) Performance in Flocculation

Maria G. Rasteiro — Fri, 27 May 2011 00:00:00 CEST

Flocculation of precipitated calcium carbonate (PCC) was monitored using light diffraction spectroscopy (LDS). Four cationic polyacrylamides of high molar mass and with different degrees of branching, all copolymers of acrylamide (AM) and acryloyloxyethyltrimethyl ammonium chloride (Q9), were tested. LDS supplied information about the kinetic curves for flocs growth and also for the flocs structure evolution. Flocculation kinetics, flocs size and structure, flocs resistance and reflocculation capacity could be correlated with the degree of branching of the polyelectrolytes (PEL). Furthermore, PEL with different degrees of branching corresponded to different values for the intrinsic viscosity, indicating differences in the polymer conformation, which explained well the performance differences in flocculation.

Polymers, Vol. 3, Pages 899-914: Synthetic Polymer Scaffolds for Stem Cell Transplantation in Retinal Tissue Engineering

Jing Yao — Thu, 26 May 2011 00:00:00 CEST

Age-related macular degeneration and retinitis pigmentosa are two leading causes of irreversible blindness characterized by photoreceptor loss. Cell transplantation may be one of the most promising approaches of retinal repair. However, several problems hinder the success of retinal regeneration, including cell delivery and survival, limited cell integration and incomplete cell differentiation. Recent studies show that polymer scaffolds can address these three problems. This article reviews the current literature on synthetic polymer scaffolds used for stem cell transplantation, especially retinal progenitor cells. The advantages and disadvantages of different polymer scaffolds, the role of different surface modifications on cell attachment and differentiation, and controlled drug delivery are discussed. The development of material and surface modification techniques is vital in making cell transplantation a clinical success.

Polymers, Vol. 3, Pages 886-898: Brillouin Scattering in Polymer Optical Fibers: Fundamental Properties and Potential Use in Sensors

Yosuke Mizuno — Thu, 26 May 2011 00:00:00 CEST

We review the fundamental properties of Brillouin scattering in a perfluorinated graded-index polymer optical fiber (PFGI-POF) with 120 μm core diameter. The experiments were performed at 1.55 μm telecommunication wavelength. The Brillouin frequency shift (BFS) and the Brillouin bandwidth were 2.83 GHz and 105 MHz, respectively. The Brillouin gain coefficient was calculated to be 3.09 × 10−11 m/W, which was comparable to that of fused silica fibers. The Brillouin threshold power of the 100 m POF was estimated to be as high as 24 W, which can be, for practical applications, reduced by using POFs with smaller cores. These properties were compared with those of silica-based graded-index multi-mode fibers. We also investigated the BFS dependences on strain and temperature. They showed negative dependences with coefficients of −121.8 MHz/% and −4.09 MHz/K, respectively, which are −0.2 and −3.5 times as large as those in silica fibers. These BFS dependences indicate that the Brillouin scattering in PFGI-POFs can be potentially applied to high-accuracy temperature sensing with reduced strain sensitivity.

Polymers, Vol. 3, Pages 875-885: A Possibility for Construction of an Iodine Cleaning System Based on Doping for π-Conjugated Polymers

Hiromasa Goto — Mon, 16 May 2011 00:00:00 CEST

An iodine accumulation method using polyaniline (PANI) and a textile composite is proposed. PANI/pulp paper sheets prepared by a paper making technique are suitable for iodine adsorption, because of good processability. The PANI-based paper sheets can be applied for iodine cleanup as air filters, water filters, and floorcloth. This concept may lead to a development of an iodine cleaning machine or iodine shield cloth based on π-conjugated polymer composites. In-situ vapor phase doping of iodine, observation of surface images, and IR measurements are carried out to examine iodine doping function for the PANI/pulp paper sheets.

Polymers, Vol. 3, Pages 861-874: Polarized Emission of Wholly Aromatic Bio-Based Copolyesters of a Liquid Crystalline Nature

Kai Kan — Mon, 16 May 2011 00:00:00 CEST

A novel thermotropic liquid crystalline polymers poly{3-benzylidene amino-4-hydroxybenzoic acid (3,4-BAHBA)-co-trans-4-hydroxycinnamic acid (4HCA: trans-coumaric acid)} (Poly(3,4-BAHBA-co-4HCA)), was synthesized by the thermal polycondensation of 4HCA and 3,4-BAHBA, which was synthesized by a reaction of 3-amino-4-hydroxybenzoic acid (3,4-AHBA) with benzaldehyde. When the 4HCA compositions of Poly(3,4-BAHBA-co-4HCA)s were above 55 mol%, the copolymers showed a nematic, liquid crystalline phase. Differential scanning calorimetry (DSC) measurements of the copolymers showed a high glass transition temperature of more than 100 °C, sufficient for use in engineering plastics. Furthermore, the copolymers showed photoluminescence in an N-methylpyrrolidone (NMP) solution under ultraviolet (UV) light with a wavelength of 365 nm. Oriented film of Poly(3,4-BAHBA-co-4HCA) with a 4HCA composition of 75 mol% emitted polarized light, which was confirmed by fluorescent spectroscopy equipped with parallel and crossed polarizers.

Polymers, Vol. 3, Pages 846-860: Rotational Diffusion of Macromolecules and Nanoparticles Modeled as Non-Overlapping Bead Arrays in an Effective Medium

Hengfu Wu — Fri, 13 May 2011 00:00:00 CEST

In this work, the retarding influence of a gel on the rotational motion of a macromolecule is investigated within the framework of the Effective Medium (EM) model. This is an extension of an earlier study that considered the effect of a gel on the translational motion of a macromolecule [Allison, S. et al. J. Phys. Chem. B 2008, 112, 5858-5866]. The macromolecule is modeled as an array of non-overlapping spherical beads with no restriction placed on their size or configuration. Specific applications include the rotational motion of right circular cylinders and wormlike chains modeled as strings of identical touching beads. The procedure is then used to examine the electric birefringence decay of a 622 base pair DNA fragment in an agarose gel. At low gel concentration (M ≤ 0.010 gm/mL), good agreement between theory and experiment is achieved if the persistence length of DNA is taken to be 65 nm and the gel fiber radius of agarose is taken to be 2.5 nm. At higher gel concentrations, the EM model substantially underestimates the rotational relaxation time of DNA and this can be attributed to the onset of direct interactions that become significant when the effective particle size becomes comparable to the mean gel fiber spacing.