In-situ impedance spectroscopy of layer-by-layer self-assembly of polyelectrolytes

In-situ impedance spectroscopy of layer-by-layer self-assembly of weak polyelectrolytes is presented. Interdigitated capacitors with active area of 1×1 mm2 and electrode spacing of 5 μm are fabricated and used for this purpose. Measurement results indicate that the impedance decreases with increase in number of polyelectrolyte layers. About 2.5% of relative change in magnitude of impedance at 104.7 KHz is seen for four bi-layers of Poly(Allylamine Hydrochloride) (PAH)/Poly(Acrylic acid) (PAA). An electrical equivalent for polyelectrolyte binding is obtained.

Stimuli-responsive weak polyelectrolyte multilayer films: A thin film platform for self triggered multi-drug delivery

Polyelectrolyte multilayer (PEM) thin film composed of weak polyelectrolytes was designed by layer-by-layer (LbL) assembly of poly(allylamine hydrochloride) (PAH) and poly(methacrylic acid) (PMA) for multi-drug delivery applications. Environmental stimuli such as pH and ionic strength showed significant influence in changing the film morphology from pore-free smooth structure to porous structure and favored triggered release of loaded molecules. The film was successfully loaded with bovine serum albumin (BSA) and ciprofloxacin hydrochloride (CH) by modulating the porous polymeric network of the film. Release studies showed that the amount of release could be easily controlled by changing the environmental conditions such as pH and ionic strength. Sustained release of loaded molecules was observed up to 8 h. The fabricated films were found to be biocompatible with epithelial cells during in-vitro cell culture studies. PEM film reported here not only has the potential to be used as self-responding thin film platform for transdermal drug delivery, but also has the potential for further development in antimicrobial or anti-inflammatory coatings on implants and drug-releasing coatings for stents. (C) 2015 Elsevier B.V. All rights reserved.

Polyelectrolyte microcapsules for sustained delivery of water-soluble drugs

Polyelectrolyte capsules composed of weak polyelectrolytes are introduced as a simple and efficient system for spontaneous encapsulation of low molecular weight water-soluble drugs. Polyelectrolyte capsules were prepared by layer-by-layer (LbL) assembling of weak polyelectrolytes, poly(allylamine hydrochloride) (PAH) and poly (methacrylic acid) (PMA) on polystyrene sulfonate (PSS) doped CaCO3 particles followed by core removal with ethylene-diaminetetraacetic add (EDTA). The loading process was observed by confocal laser scanning microscopy (CLSM) using tetramethylrhodamineisothiocyanate labeled dextran (TRITC-dextran) as a fluorescent probe. The intensity of fluorescent probe inside the capsule decreased with increase in cross-linking time. Ciprofloxacin hydrochloride (a model water-soluble drug) was spontaneously deposited into PAH/PMA capsules and their morphological changes were investigated by scanning electron microscopy (SEM) and atomic force microscopy (AFM). The quantitative study of drug loading was also elucidated which showed that drug loading increased with initial drug concentration, but decreased with increase in pH. The loaded drug was released in a sustained manner for 6 h, which could be further extended by cross-linking the capsule wall. The released drug showed significant antibacterial activity against E. coli. These findings indicate that such capsules can be potential carriers for water-soluble drugs in sustained/controlled drug delivery applications. (C) 2010 Elsevier B.V. All rights reserved.

Detection limit of etched fiber bragg grating sensors

While Fiber Bragg Grating (FBG) sensors have been extensively used for temperature and strain sensing, clad etched FBGs (EFBGs) have only recently been explored for refractive index sensing. Prior literature in EFBG based refractive index sensing predominantly deals with bulk refractometry only, where the Bragg wavelength shift of the sensor as a function of the bulk refractive index of the sample can be analytically modeled, unlike the situation for adsorption of molecular thin films on the sensor surface. We used a finite element model to calculate the Bragg wavelength change as a function of thickness and refractive index of the adsorbing molecular layer and compared the model with the real-time, in-situ measurement of electrostatic layer-by-layer (LbL) assembly of weak polyelectrolytes on the silica surface of EFBGs. We then used this model to calculate the layer thickness of LbL films and found them to be in agreement with literature. Further, we used this model to arrive at a realistic estimate of the limit of detection of EFBG sensors based on nominal measurement noise levels in current FBG interrogation systems and found that sufficiently thinned EFBGs can provide a competitive platform for real-time measurement of molecular interactions while simultaneously leveraging the high multiplexing capabilities of fiber optics.

Layer-by-Layer Buildup of Poly(L-glutamic acid)/Chitosan Film for Biologically Active Coating

A new biocompatible film based on chitosan and poly(L-glutamic acid) (CS/PGA), created by alternate deposition of CS and PGA, was investigated. FT-IR spectroscopy, UV-vis spectroscopy and QCM were used to analyze the build-up process. The growth of CS and PGA deposition are both exponential to the deposition steps at first. After about 9 (CS/PGA) depositions, the exponential to linear transition takes place. QCM measurements combined with UV-vis spectra revealed the increase in the multilayer film growth at different pH (4.4, 5.0 and 5.5). The build-up of the multilayer stops after a few depositions at pH = 6.5. A muscle myoblast cell (C2C12) assay showed that (CS/PGA)(n) multilayer films obviously promote C2C12 attachment and growth.

Counterion exchange at the surface of polyelectrolyte multilayer film for wettability modulation

Counterions present at the surface of polyelectrolyte multilayers (PEMs) were utilized for modulation of surface wettability via ion exchange. The PEM film was dipped in aqueous solutions of different anions, respectively, and the water contact angle of the surface varied from about 10 degrees to 120 degrees, depending on the hydration characteristics of the anion. The ion exchange mechanism was verified by X-ray photoelectron spectroscopy. The process was rapid and reversible. Ionic strength of the polyelectrolyte solution used for preparing the PEMs was found to be crucial to the surface wetting properties and the reversibility and kinetics of the process, and the effects were correlated to the surface density of the excess charge and counterion. This work provides a general, facile and rapid approach of surface property modulation.

Silver Nanoparticles Obtained in PAH/PAA-Based Multilayers by Photochemical Reaction

Carboxylic acid groups in PAH/PAA-based multilayers bind silver cations by ion exchange with the acid protons. The aggregation and spatial distribution of the nanoparticles proved to be dependent oil the process used to reduce the silver acetate aqueous solution. The reducing method with ambient light formed larger nanoparticles with diameters ranging from 4-50 nm in comparison with the reduction method using UV light, which gave particles with diameters of 2-4 nm The high toughness of samples reduced by ambient light is a result of two population distributions of particle sizes caused by different mechanisms when compared with the UV light process. According to these phenomena, a judicious choice of the spectral source call be used as a way to control the type and size of silver nanoparticles formed on PEMs. Depending on the energy of the light source, the Ag nanoparticles present cubic and/or hexagonal crystallographic structures, as confirmed by XRD. Beyond the kinetically controlled process of UV photoinduced cluster formation, the annealing produced by UV light allowed a second mechanism to modify the growth rates, spatial distribution, and phases.

Characterization and application of nanostructured films containing Au and TiO2 nanoparticles supported in bacterial cellulose

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Reversible and irreversible pH induced conformational changes in self-assembled weak polyelectrolyte multilayers probed using etched fiber Bragg grating sensors

Polyelectrolytes are charged polymer species which electrostatically adsorb onto surfaces in a layer by layer fashion leading to the sequential assembly of multilayer structures. It is known that the morphology of weak polyelectrolyte structures is strongly influenced by environmental variables such as pH. We created a weak polyelectrolyte multilayer structure (similar to 100 nm thick) of cationic polymer poly-allylamine hydrochloride (PAH) and an anionic polymer poly-acrylic acid (PAA) on an etched clad fiber Bragg grating (EFBG) to study the pH induced conformational transitions in the polymer multilayers brought about by the variation in charge density of weak polyelectrolyte groups as a function of pH. The conformational changes of the polyelectrolyte multilayer structure lead to changes in optical density of the adsorbed film which reflects in the shift of the Bragg wavelength from the EFBG. Using the EFBG system we were able to probe reversible and irreversible pH induced transitions in the PAH/PAA weak polyelectrolyte system. (C) 2014 Elsevier B.V. All rights reserved.

The domestic kitchen : the weak link in the food chain : is convenience leading to apathy?

To investigate the meaning and understanding of domestic food preparation within the lived experience of the household's main food preparer this ethnographic study used a combination of qualitative and quantitative methodologies. Data were collected from three sources: the literature; an in-store survey of251 food shoppers chosen at random while shopping during both peak and off peak shopping periods at metropolitan supermarkets; and semi-structured interviews with the principal food shopper and food preparer of 15 different Brisbane households. Male and female respondents representing a cross section of socio-economic groupings, ranged in age from 19-79 years and were all from English speaking backgrounds. Changes in paid labour force participation, income and education have increased the value of the respondents' time, instigating massive changes in the way they shop, cook and eat. Much of their food preparation has moved from the domestic kitchen into the kitchens of other food establishments. For both sexes, the dominant motivating force behind these changes is a combination of the their self perceived lack of culinary skill; lack of enjoyment of cooking and lack of motivation to cook. The females in paid employment emphasise all factors, particularly the latter two, significantly more than the non-employed females. All factors are of increasing importance for individuals aged less than 35 years and conversely, of significantly diminished importance to older respondents. Overall, it is the respondents aged less than 25 years who indicate the lowest cooking frequency and/or least cooking ability. Inherent in this latter group is an indifference to the art/practice of preparing food. Increasingly, all respondents want to do less cooking and/or get the cooking over with as quickly as possible. Convenience is a powerful lure by which to spend less time in the kitchen. As well, there is an apparent willingness to pay a premium for convenience. Because children today are increasingly unlikely to be taught to cook, addressing the food skills deficit and encouraging individuals to cook for themselves are significant issues confronting health educators. These issues are suggested as appropriate subjects of future research.

Stability boundary analysis of the dynamic voltage restorer in weak systems with dynamic loads

In this contribution, a stability analysis for a dynamic voltage restorer (DVR) connected to a weak ac system containing a dynamic load is presented using continuation techniques and bifurcation theory. The system dynamics are explored through the continuation of periodic solutions of the associated dynamic equations. The switching process in the DVR converter is taken into account to trace the stability regions through a suitable mathematical representation of the DVR converter. The stability regions in the Thevenin equivalent plane are computed. In addition, the stability regions in the control gains space, as well as the contour lines for different Floquet multipliers, are computed. Besides, the DVR converter model employed in this contribution avoids the necessity of developing very complicated iterative map approaches as in the conventional bifurcation analysis of converters. The continuation method and the DVR model can take into account dynamics and nonlinear loads and any network topology since the analysis is carried out directly from the state space equations. The bifurcation approach is shown to be both computationally efficient and robust, since it eliminates the need for numerically critical and long-lasting transient simulations.

Supplement : Efficient weak second-order stochastic Runge-Kutta methods for non-commutative Stratonvich stochastic differential equations

This paper gives a modification of a class of stochastic Runge–Kutta methods proposed in a paper by Komori (2007). The slight modification can reduce the computational costs of the methods significantly.

An enriched radial point interpolation method based on weak-form and strong-form

In this article, an enriched radial point interpolation method (e-RPIM) is developed for computational mechanics. The conventional radial basis function (RBF) interpolation is novelly augmented by the suitable basis functions to reflect the natural properties of deformation. The performance of the enriched meshless RBF shape functions is first investigated using the surface fitting. The surface fitting results have proven that, compared with the conventional RBF, the enriched RBF interpolation has a much better accuracy to fit a complex surface than the conventional RBF interpolation. It has proven that the enriched RBF shape function will not only possess all advantages of the conventional RBF interpolation, but also can accurately reflect the deformation properties of problems. The system of equations for two-dimensional solids is then derived based on the enriched RBF shape function and both of the meshless strong-form and weak-form. A numerical example of a bar is presented to study the effectiveness and efficiency of e-RPIM. As an important application, the newly developed e-RPIM, which is augmented by selected trigonometric basis functions, is applied to crack problems. It has been demonstrated that the present e-RPIM is very accurate and stable for fracture mechanics problems.