Sulfonation of dialdehyde cellulose extracted from sugarcane bagasse for synergistically enhanced water solubility.

Sulfonated cellulose (SC) was successfully derived from microcrystalline cellulose (MCC) extracted from sugarcane bagasse, which is a type of agricultural waste. The obtained MCC was first modified by oxidation using sodium periodate in order to cleave the carbon-carbon bonds at the C2 and C3 of the pyranose ring to form 2,3-dialdehyde cellulose. These activated aldehyde groups significantly facilitated the sulfonation carried out using potassium metabisulfite.

Polymerized Ionic Liquids: Correlation of Ionic Conductivity with Nanoscale Morphology and Counterion Volume.

The impact of the chemical structure on ion transport, nanoscale morphology, and dynamics in polymerized imidazolium-based ionic liquids is investigated by broadband dielectric spectroscopy and X-ray scattering, complemented with atomistic molecular dynamics simulations. Anion volume is found to correlate strongly with -independent ionic conductivities spanning more than 3 orders of magnitude. In addition, a systematic increase in alkyl side chain length results in about one decade decrease in -independent ionic conductivity correlating with an increase in the characteristic backbone-to-backbone distances found from scattering and simulations.

Environmental stress cracking performance of polyether and PDMS-based polyurethanes in an in vitro oxidation model.

Environmental stress cracking (ESC) was replicated in vitro on Optim™ (OPT) insulation, a polydimethylsiloxane-based polyurethane utilized clinically in cardiac leads, using a Zhao-type oxidation model. OPT performance was compared to that of two industry standard polyether urethanes: Pellethane 80A (P80A), and Pellethane 55D (P55D). Clinically relevant specimen configurations and strain states were utilized: low-voltage cardiac lead segments were held in a U-shape by placing them inside of vials.

Charge Transport of Polyester Ether Ionomers in Unidirectional Silica Nanopores.

Dielectric relaxation spectroscopy is employed to investigate charge transport properties of two polyester ether ionomers in the bulk state and when confined in unidirectional nanoporous membranes (average pore diameter = 7.5 nm). Under nanometric confinement in nonsilanized pores, the macroscopic transport quantities (dc conductivity and characteristic frequency rate) are lower by about 1.

Segmental Dynamics and Dielectric Constant of Polysiloxane Polar Copolymers as Plasticizers for Polymer Electrolytes.

Dielectric relaxation spectroscopy was used to investigate the segmental dynamics of a series of siloxane-based polar copolymers combining pendant cyclic carbonates and short poly(ethylene oxide) (PEO) chains. The homopolymer with cyclic carbonate as the only side chain exhibits higher glass transition temperature T(g) and dielectric constant ε(s) than the one with only PEO side chains. For their copolymers the observed T(g) (agreeing well with the predicted values from the Fox equation) and ε(s) decrease with increasing PEO side chain content.

The biostability of cardiac lead insulation materials as assessed from long-term human implants.

Accelerated in vitro biostability studies are useful for making relativistic comparisons between materials. However, no in vitro study can completely replicate the complex biochemical and biomechanical environment that a material experiences in the human body. To overcome this limitation, three insulation materials [Optim™ insulation (OPT), Pellethane® 55D (P55D), and silicone elastomer] from cardiac leads that were clinically implanted for up to five years were characterized using visual inspection, SEM, ATR-FTIR, GPC, and tensile testing.

Limitations of predicting in vivo biostability of multiphase polyurethane elastomers using temperature-accelerated degradation testing.

Polyurethane biostability has been the subject of intense research since the failure of polyether polyurethane pacemaker leads in the 1980s. Accelerated in vitro testing has been used to isolate degradation mechanisms and predict clinical performance of biomaterials. However, validation that in vitro methods reproduce in vivo degradation is critical to the selection of appropriate tests.

Characterizing the structure of organic molecules of intrinsic microporosity by molecular simulations and X-ray scattering.

The design of a new class of materials, called organic molecules of intrinsic microporosity (OMIMs), incorporates awkward, concave shapes to prevent efficient packing of molecules, resulting in microporosity. This work presents predictive molecular simulations and experimental wide-angle X-ray scattering (WAXS) for a series of biphenyl-core OMIMs with varying end-group geometries. Development of the utilized simulation protocol was based on comparison of several simulation methods to WAXS patterns.

Novel hard-block polyurethanes with high strength and transparency for biomedical applications.

Novel hard-block-only polyurethanes are prepared from 1,4-butanediol (BDO) and a pre-polymer synthesized separately from 1,3-bis (4-hydroxybutyl) tetramethyl disiloxane (BHTD) and 4,4'-diphenylmethane diisocyanate (MDI). Three (co)polymers using different proportions of these chain extenders were synthesized using reaction injection moulding, and their microstructure, mechanical properties and in vitro oxidative biostability were evaluated. These materials were found to form a single-phase system, and exhibit optical transparency, high elastic modulus and tensile strength, as well as significant in vitro oxidative biostability.

Dynamics of hydrated polyurethane biomaterials: Surface microphase restructuring, protein activity and platelet adhesion.

Microphase separation is a central feature of segmented polyurethane biomaterials and contributes to the biological response to these materials. In this study we utilized atomic force microscopy (AFM) to study the dynamic restructuring of three polyurethanes having soft segment chemistries of interest in biomedical applications. For each of the materials we followed the changes in near surface mechanical properties during hydration, as well as fibrinogen activity and platelet adhesion on these surfaces.

Molecular mobility and Li(+) conduction in polyester copolymer ionomers based on poly(ethylene oxide).

We investigate the segmental and local dynamics as well as the transport of Li(+) cations in a series of model poly(ethylene oxide)-based single-ion conductors with varying ion content, using dielectric relaxation spectroscopy. We observe a slowing down of segmental dynamics and an increase in glass transition temperature above a critical ion content, as well as the appearance of an additional relaxation process associated with rotation of ion pairs. Conductivity is strongly coupled to segmental relaxation.

Segmental Dynamics and Ionic Conduction in Poly(vinyl methyl ether)-Lithium Perchlorate Complexes.

Broadband dielectric spectroscopy was used to investigate the segmental dynamics and ionic conduction in LiClO4/PVME complexes with Li/O from 0.1/100 to 10/100, at temperatures from Tg to approximately Tg + 80 degrees C. Although no microphase separation is observed via DSC, dielectric experiments reveal two segmental relaxations and one localized ion motion process.

In vitro oxidation of high polydimethylsiloxane content biomedical polyurethanes: correlation with the microstructure.

The resistance to in vitro metal ion oxidation of a polydimethylsiloxane (PDMS)-containing thermoplastic polyurethane elastomer (Elast-Eon) is compared with that of a polyurethane consisting of the same hard segment chemistry and content, but with aliphatic polycarbonate soft segments (PCU). Scanning electron microscopy and attenuated total reflectance Fourier transform infrared spectroscopy were used to assess changes in surface morphology and chemistry. The extent of bulk degradation was assessed indirectly by dynamic mechanical analysis and small-angle X-ray scattering experiments.

Ion conduction and polymer dynamics of poly(2-vinylpyridine)-lithium perchlorate mixtures.

Ion conduction and polymer dynamics of homogeneous mixtures of poly(2-vinylpyridine) (P2VPy) with 0.1 to 10 mol % lithium perchlorate (LiClO(4)) were investigated using broadband dielectric spectroscopy. Interpretation of the relaxation behavior was assisted by findings from differential scanning calorimetry, Fourier transform infrared spectroscopy, dynamic mechanical analysis, and wide-angle and small-angle X-ray scattering experiments.

Plasticized single-ion polymer conductors: conductivity, local and segmental dynamics, and interaction parameters.

This paper considers high-quality conductivity data for plasticized ionomers in the context of polymer local and segmental processes. Dielectric spectroscopy was conducted on a neat PEO-based ionomer and six mixtures containing 6 wt % plasticizer with a wide range of dielectric constants. Conductivity increased dramatically but remained Vogel Fulcher Tamman (VFT)-like for all plasticized ionomers, indicating that the mechanism of ion transport was unchanged.

Characterization of surface microphase structures of poly(urethane urea) biomaterials by nanoscale indentation with AFM.

Atomic force microscopy utilizing both tapping mode and force mode imaging is used to visualize the separated microphases in poly(urethane urea) films under ambient and aqueous conditions. The topography of the PUU surface changed upon hydration with the formation of nanometer-sized features on the surface. The surface becomes enriched in hard domains with hydration time and this enrichment is irreversible after dehydration.

Human foetal osteoblastic cell response to polymer-demixed nanotopographic interfaces.

Nanoscale cell-substratum interactions are of significant interest in various biomedical applications. We investigated human foetal osteoblastic cell response to randomly distributed nanoisland topography with varying heights (11, 38 and 85 nm) produced by a polystyrene (PS)/polybromostyrene polymer-demixing technique. Cells displayed island-conforming lamellipodia spreading, and filopodia projections appeared to play a role in sensing the nanotopography.

Modeling electrode polarization in dielectric spectroscopy: Ion mobility and mobile ion concentration of single-ion polymer electrolytes.

A novel method is presented whereby the parameters quantifying the conductivity of an ionomer can be extracted from the phenomenon of electrode polarization in the dielectric loss and tan delta planes. Mobile ion concentrations and ion mobilities were determined for a poly(ethylene oxide)-based sulfonated ionomer with Li(+), Na(+), and Cs(+) cations. The validity of the model was confirmed by examining the effects of sample thickness and temperature.

Amylose crystallization from concentrated aqueous solution.

Maize amylose, separated from granular starch by means of an aqueous leaching process, was used to investigate spherulite formation from concentrated mixtures of starch in water. Amylose (10-20%, w/w) was found to form a spherulitic semicrystalline morphology over a wide range of cooling rates (1-250 degrees C/min), provided it was first heated to >170 degrees C. This is explained through the effect of temperature on chain conformation.

Atomic force microscopy visualization of poly(urethane urea) microphase rearrangements under aqueous environment.

Polyurethane biomaterials are a critically important class of polymers used in a variety of medical devices. It has been suggested that the good blood compatibility of polyurethanes arises from nanoscale chemical heterogeneities at the surface as a consequence of the microphase separated morphology. In this study, we used tapping mode atomic force microscopy with phase imaging under aqueous conditions to visualize the distribution of the surface microphases for a series of poly(urethane urea) block co-polymers with varying hard segment content.

Spherulitic crystallization in starch as a model for starch granule initiation.

The influence of cooling rate and quench temperature on the formation of spherulitic morphology in heated mung bean starch is reported. Spherulites were obtained for a wide range of cooling rates (2.5-250 degrees C/min), provided the system was heated to 180 degrees C and then cooled below 65 degrees C.

Solid-state microstructure of poly(l-lactide) and l-lactide/meso-lactide random copolymers by atomic force microscopy (AFM).

Tapping mode atomic force microscopy was used to investigate the lamellar morphology of poly(l-lactide) and two poly(l-lactide-co-meso-lactide) random copolymers containing 3% and 6% meso-lactide. Samples were isothermally crystallized at selected temperatures, and qualitative and quantitative analyses of lamellar structure were performed using height and phase images. This is the first study of the morphology of polylactide stereocopolymers using a real-space probe, and the important effects of scanning parameters on the acquired images are described.

Low permeability biomedical polyurethane nanocomposites.

In this article we describe our continuing research on a novel nanocomposite approach for reducing gas permeability through biomedical polyurethane membranes. Nanocomposites were prepared using commercially available poly(urethane urea)s (PUU) and two organically modified layered silicates (OLS). Wide-angle X-ray diffraction experiments showed that the silicate layer spacing in the nanocomposites increased significantly compared with the neat OLS, signifying the formation of intercalated PUU/OLS structures.