Development of a nanoporous and multilayer drug-delivery platform for medical implants.

Biodegradable polymers can be applied to a variety of implants for controlled and local drug delivery. The aim of this study is to develop a biodegradable and nanoporous polymeric platform for a wide spectrum of drug-eluting implants with special focus on stent-coating applications. It was synthesized by poly(DL-lactide-co-glycolide) (PLGA 65:35, PLGA 75:25) and polycaprolactone (PCL) in a multilayer configuration by means of a spin-coating technique. The antiplatelet drug dipyridamole was loaded into the surface nanopores of the platform. Surface characterization was made by atomic force microscopy (AFM) and spectroscopic ellipsometry (SE). Platelet adhesion and drug-release kinetic studies were then carried out. The study revealed that the multilayer films are highly nanoporous, whereas the single layers of PLGA are atomically smooth and spherulites are formed in PCL. Their nanoporosity (pore diameter, depth, density, surface roughness) can be tailored by tuning the growth parameters (eg, spinning speed, polymer concentration), essential for drug-delivery performance. The origin of pore formation may be attributed to the phase separation of polymer blends via the spinodal decomposition mechanism. SE studies revealed the structural characteristics, film thickness, and optical properties even of the single layers in the triple-layer construct, providing substantial information for drug loading and complement AFM findings. Platelet adhesion studies showed that the dipyridamole-loaded coatings inhibit platelet aggregation that is a prerequisite for clotting. Finally, the films exhibited sustained release profiles of dipyridamole over 70 days. These results indicate that the current multilayer phase therapeutic approach constitutes an effective drug-delivery platform for drug-eluting implants and especially for cardiovascular stent applications.

Nanoengineering coaxial carbon nanotube-dual-polymer heterostructures.

We describe studies of new nanostructured materials consisting of carbon nanotubes wrapped in sequential coatings of two different semiconducting polymers, namely, poly(3-hexylthiophene) (P3HT) and poly(9,9'-dioctylfluorene-co-benzothiadiazole) (F8BT). Using absorption spectroscopy and steady-state and ultrafast photoluminescence measurements, we demonstrate the role of the different layer structures in controlling energy levels and charge transfer in both solution and film samples. By varying the simple solution processing steps, we can control the ordering and proportions of the wrapping polymers in the solid state. The resulting novel coaxial structures open up a variety of new applications for nanotube blends and are particularly promising for implementation into organic photovoltaic devices. The carbon nanotube template can also be used to optimize both the electronic properties and morphology of polymer composites in a much more controlled fashion than achieved previously, offering a route to producing a new generation of polymer nanostructures.

Effect of polymer concentration on stabilized large-tilt-angle flexoelectro-optic switching

In this letter, the uniform lying helix (ULH) liquid crystal texture, required for the flexoelectro-optic effect, is polymer stabilized by the addition of a small percentage of reactive mesogen to a high-tilt-angle (φ>60°) bimesogenic chiral nematic host. The electro-optic response is measured for a range of reactive mesogen concentration mixtures, and compared to the large-tilt-angle switch of the pure chiral nematic mixture. The optimum concentration of reactive mesogen, which is found to provide ample stabilization of the texture with minimal impact on the electro-optic response, is found to be approximately 3%. Our results indicate that polymer stabilization of the ULH texture using a very low concentration of reactive mesogen is a reliable way of ruggedizing flexoelectro-optic devices without interfering significantly with the electro-optics of the effect, negating the need for complicated surface alignment patterns or surface-only polymerization. The polymer stabilization is shown to reduce the temperature dependence of the flexoelectro-optic response due to "pinning" of the chiral nematic helical pitch. This is a restriction of the characteristic thermochromic behavior of the chiral nematic. Furthermore, selection of the temperature at which the sample is ultraviolet cured allows the tilt angle to be optimized for the entire chiral nematic temperature range. The response time, however, remains more sensitive to operating temperature than curing temperature. This allows the sample to be cured at low temperature and operated at high temperature, providing simultaneous optimization of these two previously antagonistic performance aspects. © 2006 American Institute of Physics.

A comparative study of plasma-enhanced chemical vapor gate dielectrics for solution-processed polymer thin-film transistor circuit integration

This paper considers plasma-enhanced chemical vapor deposited (PECVD) silicon nitride (SiNx) and silicon oxide (SiOx) as gate dielectrics for organic thin-film transistors (OTFTs), with solution-processed poly[5, 5′ -bis(3-dodecyl-2-thienyl)-2, 2′ -bithiophene] (PQT-12) as the active semiconductor layer. We examine transistors with SiNx films of varying composition deposited at 300 °C as well as 150 °C for plastic compatibility. The transistors show over 100% (two times) improvement in field-effect mobility as the silicon content in SiNx increases, with mobility (μFE) up to 0.14 cm2 /V s and on/off current ratio (ION / IOFF) of 108. With PECVD SiOx gate dielectric, preliminary devices exhibit a μFE of 0.4 cm2 /V s and ION / IOFF of 108. PQT-12 OTFTs with PECVD SiNx and SiOx gate dielectrics on flexible plastic substrates are also presented. These results demonstrate the viability of using PECVD SiN x and SiOx as gate dielectrics for OTFT circuit integration, where the low temperature and large area deposition capabilities of PECVD films are highly amenable to integration of OTFT circuits targeted for flexible and lightweight applications. © 2008 American Institute of Physics.

Mechanically tunable conjugated polymer distributed feedback lasers

Herein we report a low-threshold organic laser device based on semiconducting poly(9, 9′ -dioctylfluoren-2,7-diyl-alt-benzothiadiazole) (F8BT) encapsulated in a mechanically stretchable polydimethylsiloxane (PDMS) matrix. We take advantage of the natural flexibility of PDMS to alter the periodicity of the distributed feedback grating which in turn tunes the gain wavelength at which the resonant feedback is obtained. This way, we demonstrate that low-threshold lasing [6.1 μJ cm-2 (5.3 nJ)] is maintained over a large stretching range of 0%-7% which translates into a tuning range of about 20 nm. © 2010 American Institute of Physics.

Normally closed microgrippers based on diamond-like carbon/Ni bimorph and diamond-like carbon/metal/polymer trimorph structures

Multi-finger, normally-closed microgrippers made from a bilayer of a metal and diamond-like carbon (DLC) or a trilayer of a polymer, metal and DLC have been analysed, simulated and fabricated. Temperatures of ∼700 K are necessary to open Ni/DLC bimorph structures. Microgrippers made from an SU8/DLC bilayer or SU8/Al/DLC trilayer have also been fabricated, and fully closed microcages with diameters of ∑40 μm have been obtained. Using SU8 reduces the opening temperature of these devices to only ∼400 K.

Dispersion rheology of carbon nanotubes in a polymer matrix

We report on rheological properties of a dispersion of multiwalled carbon nanotubes in a viscous polymer matrix. Particular attention is paid to the process of nanotubes mixing and dispersion, which we monitor by the rheological signature of the composite. The response of the composite as a function of the dispersion mixing time and conditions indicates that a critical mixing time t* needs to be exceeded to achieve satisfactory dispersion of aggregates, this time being a function of nanotube concentration and the mixing shear stress. At shorter times of shear mixing t< t*, we find a number of nonequilibrium features characteristic of colloidal glass and jamming of clusters. A thoroughly dispersed nanocomposite, at t> t*, has several universal rheological features; at nanotube concentration above a characteristic value nc ∼2-3 wt. % the effective elastic gel network is formed, while the low-concentration composite remains a viscous liquid. We use this rheological approach to determine the effects of aging and reaggregation. © 2006 The American Physical Society.

Electron microscopy of polymer-carbon nanotubes composites

Characterization of polymer nanocomposites by electron microscopy has been attempted since last decade. Main drives for this effort were analysis of dispersion and alignment of fillers in the matrix. Sample preparation, imaging modes and irradiation conditions became particularly challenging due to the small dimension of the fillers and also to the mechanical and conductive differences between filler and matrix. To date, no standardized dispersion and alignment process or characterization procedures exist in the trade. Review of current state of the art on characterization of polymer nanocomposites suggests that the most innovative electron and ion beam microscopy has not yet been deployed in this material system. Additionally, recently discovered functionalities of these composites, such as electro and photoactuation are amenable to the investigation of the atomistic phenomena by in situ transmission electron microscopy. The possibility of using innovative thinning techniques is presented. © 2010 Copyright SPIE - The International Society for Optical Engineering.

Tailoring the electrical properties of carbon nanotube-polymer composites

Advances in functionality and reliability of nanocomposite materials require careful formulation of processing methods to ultimately realize the desired properties. An extensive study of how the variation in fabrication process would affect the mechanism of conductivity and thus the final electrical properties of the carbon nanotube-polymer composite is presented. Some of the most widely implemented procedures are addressed, such as ultrasonication, melt shear mixing, and addition of surfactants. It is hoped that this study could provide a systematic guide to selecting and designing the downstream processing of carbon nanocomposites. Finally, this guide is used to demonstrate the fabrication and performance of a stretchable (pliable) conductor that can reversibly undergo uniaxial strain of over 100%, and other key applications are discussed. © 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Multi-colour switching of polymer stabilized chiral nematic liquid crystal devices

We have fabricated a series of polymer stabilized chiral nematic test cells for use as flexoelectro-optic devices. The devices fabricated were based on commercial chiral nematic mixtures which were polymer stabilized so as to enhance the uniformity and stability of the uniform lying helix texture in the cells. During fabrication and test procedures a series of unusual scattering states have been observed within the devices at different viewing angles. The observations made so far indicate that the properties of the scattering state lies somewhere between the focal conic texture and the Grandjean or planar texture and that the devices exhibit both a helical pitch selective reflection and scattering effect. What is even more dramatic is that the wavelength selectivity of the scattering effect can be tuned by an applied field. In addition, we show that it is possible to achieve good uniform lying helix textures from such devices. Moreover, we show that in certain cases the spontaneous alignment of the helix in the plane of the device opens up the possibility of a new mode of switching. Flexoelectric, Redshift, Coloured scattering, Liquid crystal, Polymer-stabilized liquid-crystal;.