Silicification and biosilicification : part 2. Silicification at pH 7 in the presence of a cationically charged polymer in solution and immobilized on substrates

Biosilicification is facilitated by proteins and occurs under modest conditions in an aqueous medium (pH 7 and ambient temperature). Silicification at neutral pH in vitro has been shown to occur in the presence of various cationically charged synthetic macromolecules in solution. Here, the synthesis of silica from an aqueous silica precursor in the presence of poly(allylamine hydrochloride) (PAH) and polyacrylic acid (PAA) both in solution and immobilized on substrates is investigated. The results show that the formation of ordered silica structures under these modest conditions was favored for the PAH and the PAH-PAA in solution but neither for PAA in solution nor when the polymers were immobilized as PAH-PAA bilayers on flat substrates. It is possible that the immobilization of the PAH by the electrostatically self-assembly (ESA) technique may allow it to retain its catalytic function, while not allowing it to fulfill its role as a template / structure directing agent. The silica structures were characterized using scanning electron microscope (SEM) and energy dispersive spectroscopy (EDS). For the PAH system in solution silica spheres were seen and for PAH-PAA in solution hexagonal silica structures were observed in co-existence with silica spheres. The results presented herein may be helpful in elucidating biosilicification mechanism(s) and should lead to a better understanding of silicification

Synthesis of C-60 fullerene-silica hybrid nano structures

We have recently demonstrated a procedure for the synthesis of silica nanometer and micrometer particles under modest conditions. Here we report the synthesis of C-60 fullerene-silica hybrid nanometer sized materials via sol-gel processing at neutral pH and under ambient conditions. The C-60 fullerene, when functionalized was water-soluble and also able to facilitate the formation of silica structures from an aqueous silica precursor. This C-60 fullerene had similar functinality to the cationically charged polymers, which have been reported earlier to act as catalysts/templates for silicification. The resulting organic-inorganic hybrid was studied using SEM, EDS and UV/Vis spectroscopy. These hybrid materials may have applications in areas such as optical devices, semiconductors, chemical sensors, catalysis and in the medical field. The results presented in this study may be useful in developing a process for the synthesis of novel organic-inorganic nanometer sized materials and for the biomimetic synthesis of silica

Gold Nanorod Enhanced Organic Photovoltaics: The Importance of Morphology Effects

Organic photovoltaic devices with a 30% improvement in power conversion efficiency are achieved when gold nanorods (Au NR) are incorporated into the active bulk heterojunction (BHJ) layer. Detailed analysis of the system is provided through microscopy, device characterization, and spectroscopy, demonstrating that the enhancement effects are predominantly caused by induced morphology changes in the BHJ film rather than plasmonic effects. Wide angle X-ray diffraction provides evidence that the nanorods loaded into the BHJ film have an effect on polymer crystal orientation, leading to a systematic performance increase in the devices as a result of both internal and external efficiency improvements

Dielectric Breakdown in Silica–Amorphous Polymer Nanocomposite Films: The Role of the Polymer Matrix

The ultimate energy storage performance of an electrostatic capacitor is determined by the dielectric characteristics of the material separating its conductive electrodes. Polymers are commonly employed due to their processability and high breakdown strength; however, demands for higher energy storage have encouraged investigations of ceramic–polymer composites. Maintaining dielectric strength, and thus minimizing flaw size and heterogeneities, has focused development toward nanocomposite (NC) films; but results lack consistency, potentially due to variations in polymer purity, nanoparticle surface treatments, nanoparticle size, and film morphology. To experimentally establish the dominant factors in broad structure–performance relationships, we compare the dielectric properties for four high-purity amorphous polymer films (polymethyl methacrylate, polystyrene, polyimide, and poly-4-vinylpyridine) incorporating uniformly dispersed silica colloids (up to 45% v/v). Factors known to contribute to premature breakdownfield exclusion and agglomerationhave been mitigated in this experiment to focus on what impact the polymer and polymer–nanoparticle interactions have on breakdown. Our findings indicate that adding colloidal silica to higher breakdown strength amorphous polymers (polymethyl methacrylate and polyimide) causes a reduction in dielectric strength as compared to the neat polymer. Alternatively, low breakdown strength amorphous polymers (poly-4-vinylpyridine and especially polystyrene) with comparable silica dispersion show similar or even improved breakdown strength for 7.5–15% v/v silica. At ∼15% v/v or greater silica content, all the polymer NC films exhibit breakdown at similar electric fields, implying that at these loadings failure becomes independent of polymer matrix and is dominated by silica

Electrical Detection of Self-Assembled Polyelectrolyte Multilayers by a Thin Film Resistor

The build up of polyelectrolyte multilayers (PEMs) was observed by a silicon-on-insulator (SOI) based thin film resistor. Differently charged polyelectrolytes adsorbing to the sensor surface result in defined potential shifts, which decrease with the number of layers deposited. We model the response of the device assuming electrostatic screening of polyelectrolyte charges by mobile ions within the PEMs. The Debye screening length inside the PEMs was found to be increased compared to the value corresponding to the bulk solution. Furthermore the partitioning of mobile ions between the bulk phase and the polyelectrolyte film was employed to calculate the dielectric constant of the PEMs and the concentration of mobile charges.Comment: 18 pages, 5 figure

Dielectric Breakdown Strength of Regenerated Silk Fibroin Films as a Function of Protein Conformation

Derived from Bombyx mori cocoons, regenerated silk fibroin (RSF) exhibits excellent biocompatibility, high toughness, and tailorable biodegradability. Additionally, RSF materials are flexible, optically clear, easily patterned with nanoscale features, and may be doped with a variety bioactive species. This unique combination of properties has led to increased interest in the use of RSF in sustainable and biocompatible electronic devices. In order to explore the applicability of this biopolymer to the development of future bioelectronics, the dielectric breakdown strength (<i>E</i>_bd) of RSF thin films was quantified as a function of protein conformation. The application of processing conditions that increased β-sheet content (as determined by FTIR analysis) and produced films in the silk II structure resulted in RSF materials with improved <i>E</i>_bd with values reaching up to 400 V/μm

Polyelectrolyte multilayer electrostatic gating of graphene field-effect transistors

We apply polyelectrolyte multilayer films by consecutive alternate adsorption of positively charged polyallylamine hydrochloride and negatively charged sodium polystyrene sulfonate to the surface of graphene field effect transistors. Oscillations in the Dirac voltage shift with alternating positive and negative layers clearly demonstrate the electrostatic gating effect in this simple model system. A simple electrostatic model accounts well for the sign and magnitude of the Dirac voltage shift. Using this system, we are able to create p-type or n-type graphene at will. This model serves as the basis for understanding the mechanism of charged polymer sensing using graphene devices, a potentially technologically important application of graphene in areas such as DNA sequencing, biomarker assays for cancer detection, and other protein sensing applications