Cheminanotechnology: Nanotechnology for Chemistry and Chemical Engineering

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Studies of the microstructure of polymer-modified bitumen emulsions using confocal laser scanning microscopy

Polymer-modified bitumen emulsions present a safer and more environmentally friendly binder for enhancing the properties of roads. Cationic bitumen emulsion binders containing polymer latex were investigated using confocal laser scanning microscopy. The latex was incorporated into the bitumen emulsion by using four different addition methods and all emulsions were processed with a conventional colloid mill. The emulsion binder films were studied after evaporation of the emulsion aqueous phase. We show how the microstructure and distribution of the polymer varies within the bitumen binder depending on latex addition method, and that the microstructure of the binder remains intact when exposed to elevated temperature. It was found that a distinctly fine dispersion of polymer results when the polymer is blended into the bitumen before the emulsifying process (a monophase emulsion). In contrast, bi-phase emulsion binders produced by either post-adding the latex to the bitumen emulsion, or by adding the latex into the emulsifier solution phase before processing, or by comilling the latex with the bitumen, water and emulsifier all resulted in a network formation of bitumen particles surrounded by a continuous polymer film. The use of emulsified binders appears to result in a more evenly distributed polymer network compared to the use of hot polymer-modified binders, and they therefore have greater potential for consistent binder cohesion strength, stone retention and therefore improved pavement performance

Stretching single polysaccharide molecules using AFM: A potential method for the investigation of the intermolecular uronate distribution of alginate?

Illustrative examples of the way in which the molecular force-extension behaviour of polysaccharides is governed by the nature of the linkage between their constituent pyranose rings are presented for a series of standard homopolymers. These results agree with previously proposed general hypotheses regarding the possibility of generating force-induced conformational transitions, and with the predictions of a model in which the inter-conversion of pyranose conformers is assumed to be an equilibrium process on the timescale of the molecular stretching. Subsequently, we investigate the potential of the technique in the characterisation of co-polymeric polysaccharides in which the nature of the glycan linkages is different between the two distinct residue types. Specifically, we explore the possibility that the ratio of mannuronic acid (M) to guluronic acid (G) in alginate chains will be reflected in their single molecule stretching behaviour, owing to their contrasting equatorial and axial linkages. Furthermore, as the technique described interrogates the sample one polymer at a time we outline the promise of, and the obstacles to, obtaining a new level of characterisation using this methodology where differences observed in the single molecule stretching curves obtained from single alginate samples reflectsomething of the real intermolecular distribution of the M / G ratio

A Glucose BioFuel Cell Implanted in Rats

Powering future generations of implanted medical devices will require cumbersome transcutaneous energy transfer or harvesting energy from the human body. No functional solution that harvests power from the body is currently available, despite attempts to use the Seebeck thermoelectric effect, vibrations or body movements. Glucose fuel cells appear more promising, since they produce electrical energy from glucose and dioxygen, two substrates present in physiological fluids. The most powerful ones, Glucose BioFuel Cells (GBFCs), are based on enzymes electrically wired by redox mediators. However, GBFCs cannot be implanted in animals, mainly because the enzymes they rely on either require low pH or are inhibited by chloride or urate anions, present in the Extra Cellular Fluid (ECF). Here we present the first functional implantable GBFC, working in the retroperitoneal space of freely moving rats. The breakthrough relies on the design of a new family of GBFCs, characterized by an innovative and simple mechanical confinement of various enzymes and redox mediators: enzymes are no longer covalently bound to the surface of the electron collectors, which enables use of a wide variety of enzymes and redox mediators, augments the quantity of active enzymes, and simplifies GBFC construction. Our most efficient GBFC was based on composite graphite discs containing glucose oxidase and ubiquinone at the anode, polyphenol oxidase (PPO) and quinone at the cathode. PPO reduces dioxygen into water, at pH 7 and in the presence of chloride ions and urates at physiological concentrations. This GBFC, with electrodes of 0.133 mL, produced a peak specific power of 24.4 µW mL−1, which is better than pacemakers' requirements and paves the way for the development of a new generation of implantable artificial organs, covering a wide range of medical applications

Mechanical model for a collagen fibril pair in extracellular matrix

In this paper, we model the mechanics of a collagen pair in the connective tissue extracellular matrix that exists in abundance throughout animals, including the human body. This connective tissue comprises repeated units of two main structures, namely collagens as well as axial, parallel and regular anionic glycosaminoglycan between collagens. The collagen fibril can be modeled by Hooke's law whereas anionic glycosaminoglycan behaves more like a rubber-band rod and as such can be better modeled by the worm-like chain model. While both computer simulations and continuum mechanics models have been investigated the behavior of this connective tissue typically, authors either assume a simple form of the molecular potential energy or entirely ignore the microscopic structure of the connective tissue. Here, we apply basic physical methodologies and simple applied mathematical modeling techniques to describe the collagen pair quantitatively. We find that the growth of fibrils is intimately related to the maximum length of the anionic glycosaminoglycan and the relative displacement of two adjacent fibrils, which in return is closely related to the effectiveness of anionic glycosaminoglycan in transmitting forces between fibrils. These reveal the importance of the anionic glycosaminoglycan in maintaining the structural shape of the connective tissue extracellular matrix and eventually the shape modulus of human tissues. We also find that some macroscopic properties, like the maximum molecular energy and the breaking fraction of the collagen, are also related to the microscopic characteristics of the anionic glycosaminoglycan

Wet Adhesion and Adhesive Locomotion of Snails on Anti-Adhesive Non-Wetting Surfaces

Creating surfaces capable of resisting liquid-mediated adhesion is extremely difficult due to the strong capillary forces that exist between surfaces. Land snails use this to adhere to and traverse across almost any type of solid surface of any orientation (horizontal, vertical or inverted), texture (smooth, rough or granular) or wetting property (hydrophilic or hydrophobic) via a layer of mucus. However, the wetting properties that enable snails to generate strong temporary attachment and the effectiveness of this adhesive locomotion on modern super-slippy superhydrophobic surfaces are unclear. Here we report that snail adhesion overcomes a wide range of these microscale and nanoscale topographically structured non-stick surfaces. For the one surface which we found to be snail resistant, we show that the effect is correlated with the wetting response of the surface to a weak surfactant. Our results elucidate some critical wetting factors for the design of anti-adhesive and bio-adhesion resistant surfaces

Smart Skin Patterns Protect Springtails

Springtails, arthropods who live in soil, in decaying material, and on plants, have adapted to demanding conditions by evolving extremely effective and robust anti-adhesive skin patterns. However, details of these unique properties and their structural basis are still unknown. Here we demonstrate that collembolan skin can resist wetting by many organic liquids and at elevated pressures. We show that the combination of bristles and a comb-like hexagonal or rhombic mesh of interconnected nanoscopic granules distinguish the skin of springtails from anti-adhesive plant surfaces. Furthermore, the negative overhang in the profile of the ridges and granules were revealed to be a highly effective, but as yet neglected, design principle of collembolan skin. We suggest an explanation for the non-wetting characteristics of surfaces consisting of such profiles irrespective of the chemical composition. Many valuable opportunities arise from the translation of the described comb-like patterns and overhanging profiles of collembolan skin into man-made surfaces that combine stability against wear and friction with superior non-wetting and anti-adhesive characteristics

Preparation of TiO2 Anatase Nanocrystals by TiCl4 Hydrolysis with Additive H2SO4

A new methodology was developed to synthesize uniform titania anatase nanocrystals by the hydrolysis of titanium chloride in sulfuric acid aqueous solutions at 0–90°C. The samples were characterized by Raman spectroscopy, UV-visible spectroscopy, transmission electron microscopy (TEM), electron diffraction (ED), and an Energy dispersive X-ray spectroscopy (EDS). The effects of the reaction temperature, mole ratio of SO42− to Ti4+, and the calcinations temperature on the particle size and crystal phase were investigated. Depending on the acidity, the hydrolysis temperature, and the calcination temperature, rhombic anatase nanocrystals sizes in the range of 10 nm to 50 nm were obtained. In the additive of sulfuric acid, Raman spectra and electron diffraction confirmed that the nanoparticles are composed of anatase TiO2. No other titania phases, such as rutile or brookite, were detected

Cd2+ Toxicity to a Green Alga Chlamydomonas reinhardtii as Influenced by Its Adsorption on TiO2 Engineered Nanoparticles

In the present study, Cd2+ adsorption on polyacrylate-coated TiO2 engineered nanoparticles (TiO2-ENs) and its effect on the bioavailability as well as toxicity of Cd2+ to a green alga Chlamydomonas reinhardtii were investigated. TiO2-ENs could be well dispersed in the experimental medium and their pHpzc is approximately 2. There was a quick adsorption of Cd2+ on TiO2-ENs and a steady state was reached within 30 min. A pseudo-first order kinetics was found for the time-related changes in the amount of Cd2+ complexed with TiO2-ENs. At equilibrium, Cd2+ adsorption followed the Langmuir isotherm with the maximum binding capacity 31.9, 177.1, and 242.2 mg/g when the TiO2-EN concentration was 1, 10, and 100 mg/l, respectively. On the other hand, Cd2+ toxicity was alleviated in the presence of TiO2-ENs. Algal growth was less suppressed in treatments with comparable total Cd2+ concentration but more TiO2-ENs. However, such toxicity difference disappeared and all the data points could be fitted to a single Logistic dose-response curve when cell growth inhibition was plotted against the free Cd2+ concentration. No detectable amount of TiO2-ENs was found to be associated with the algal cells. Therefore, TiO2-ENs could reduce the free Cd2+ concentration in the toxicity media, which further lowered its bioavailability and toxicity to C. reinhardtii

In Vivo Dynamics of the Musculoskeletal System Cannot Be Adequately Described Using a Stiffness-Damping-Inertia Model

Background: Visco-elastic properties of the (neuro-)musculoskeletal system play a fundamental role in the control of posture and movement. Often, these properties are described and identified using stiffness-damping-inertia (KBI) models. In such an approach, perturbations are applied to the (neuro-)musculoskeletal system and subsequently KBI-model parameters are optimized to obtain a best fit between simulated and experimentally observed responses. Problems with this approach may arise because a KBI-model neglects critical aspects of the real musculoskeletal system. Methodology/Principal Findings: The purpose of this study was to analyze the relation between the musculoskeletal properties and the stiffness and damping estimated using a KBI-model, to analyze how this relation is affected by the nature of the perturbation and to assess the sensitivity of the estimated stiffness and damping to measurement errors. Our analyses show that the estimated stiffness and damping using KBI-models do not resemble any of the dynamical parameters of the underlying system, not even when the responses are very accurately fitted by the KBI-model. Furthermore, the stiffness and damping depend non-linearly on all the dynamical parameters of the underlying system, influenced by the nature of the perturbation and the time interval over which the KBI-model is optimized. Moreover, our analyses predict a very high sensitivity of estimated parameters to measurement errors. Conclusions/Significance: The results of this study suggest that the usage of stiffness-damping-inertia models t