Some Observations of Diatoms Under Turbulence

The effect of turbulence on several freshwater diatom taxa was investigated and our findings are described herein. We have compared diatom morphology in shallow natural systems that experience turbulence due to wind and in river/waterfall systems where turbulence is due to high flow rates. We have also introduced turbulence into diatom laboratory cultures by mechanical shaking and by forcing air into the media. In particular, we have studied diatoms in five independent environments or cultures: the freshwater diatoms Tabellaria and Eunotia in equatorial lakes experiencing extreme seasonal variability in depth; two freshwater diatom monocultures of Aulacoseira granulata var angustissima and Melosira varians in the laboratory; and a freshwater diatom community possessing equal amounts (by number) of elongated and non-elongated diatoms (mostly Nitzschia and mostly Cyclotella, respectively) in the laboratory. We have demonstrated the effect of turbulence on freshwater diatom frustule morphologies and, perhaps more importantly, the effect of turbulence on freshwater diatom species population after controlled perturbation of the organisms’ environment. It has been widely reported that symmetry is often preferred in biological evolution, however here we have observed a preference towards asymmetry for the survival of diatoms in the presence of environmental stress (in particular, turbulence). We also note that to date there have been no systematic attempts to manipulate diatom frustules using external stimuli. We therefore present a proof-of-concept study in order to demonstrate: (i) that diatom morphologies can be manipulated by controlled simple external triggers (chemical and physical) (ii) that population balance (i.e. natural selection) can be controlled via simple external triggers (chemical and physical). This approach could open up an entire new field of future studies wherein controlled environmental perturbations are used to manipulate the structure, form, growth and reproduction of biological species.     

The kinetics of copper corrosion in nitric acid

The strategy for the permanent disposal of high-level nuclear waste in Canada involves sealing it in a copper-coated steel container and burying it in a deep geologic repository. During the early emplacement period, the container could be exposed to warm humid air, which could result in the condensation of nitric acid, produced by the radiolysis of the humid air, on the copper surface. Previous studies have suggested that both nitrate and oxygen reduction will drive copper corrosion, with the nitrate reduction kinetics being dependent on the concentration of soluble copper(I) produced by the anodic dissolution of copper in the reaction with oxygen. This study focused on determining the kinetics of nitrate and oxygen reduction and elucidating the synergistic relationship between the two processes. This was investigated using corrosion potential and polarization measurements in conjunction with scanning electron microscopy and X-ray photoelectron spectroscopy. Oxygen reduction was shown to be the dominant cathodic reaction with the oxidation of copper(I) to copper(II) by nitrate, promoting the catalytic cycle involving the reaction of copper(II) with copper to reproduce copper(I).     

Characterisation of polyurethane networks based on vegetable derived polyol

A polyurethane (PU) network based on vegetable derived polyol has been characterised and compared to a synthetic based network. Fracture mechanics studies showed the lowest tear strength for the vegetable networks, which decreased as molecular weight of the vegetable based polyol increased. Swelling studies were carried out to determine the molecular weight between crosslinks and polymer networks made from wholly synthetic polyols were shown to have higher molecular weight between crosslinks. Moreover, vegetable networks showed higher solubles' content. Sol-fractions were analysed by several techniques. It was found that vegetable networks based sol-fraction was mainly its correspondent raw polyol while low molecular weight oligomers were detected for the most part in synthetic networks based sol-fraction.     

Inverse gas chromatography for the determination of the dispersive surface free energy and acid–base interactions of a sheet molding compound. I. Matrix material and glass

Sheet molding compound is a material composed of a polyester thermosetting matrix with a thermoplastic, an inorganic filler, a metal oxide, reinforcement fibers, and material performance enhancers embedded in the crosslinked matrix. To achieve the optimum mechanical properties required for the composite material, the surface free energy of the polyester composite needs to be understood. In this study, the composite matrix and glass reinforcement fibers are compared with respect to their surface free energy and acid–base characteristics on the basis of inverse gas chromatography measurements. The inverse gas chromatography results for the matrix and glass are compared to previous results found for sized and unsized cellulosic fibers. The inverse gas chromatography data are used to assess chemical modifications performed on the biobased fibers to predict improvements in the fiber/matrix interaction, and this provides inferences on the overall composite cohesion. Our results show first that any fiber reinforcement system for the polyester composite material has to be acidic to promote good adhesion as the matrix system is very basic and second that the individual dispersive surface energies of the components of the matrix interact in a weighted average to determine the overall surface energy of the composite. Also, a commercial glass reinforcement sized for polyester has been found to have a lower interaction parameter than literature values for cellulosic fibers. This finding suggests that cellulosic fibers might have an advantage in competing with a conventional glass‐fiber reinforcement system in fiber/matrix bonding for sheet molding compound composites. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Application of one-dimensional mechanical formulations to model the sagging behavior of a polymer sheet

The deformation of a heated plastic sheet clamped on two opposite sides subject to sagging under its own weight was examined experimentally and then modeled using two separate one-dimensional approaches based upon cable (membrane) and beam formulations. The cable formulation neglects both bending and shear deformation, but includes a generalized Maxwell viscoelastic constitutive model to capture the time-dependent nature of sheet sag. The resulting equations are integrated using a Runge-Kutta technique and solved via a shooting method. The beam formulation is based upon the Timoshenko theory and thus includes shear deformation along with the flexural contributions. A finite element method is developed from application of the principle of virtual work for the beam written in curvilinear coordinates in order to include the effects of finite deformation. A generalized Maxwell model is again employed to account for the time-dependent material response. In both formulations, the method of reduced variables is used to describe the variation of material response with temperature. The effect of temperature and thermal relaxation is included. The particular case of a styrenic material is discussed in detail.     

Effect of thermal degradation on the impact properties of PVC compounds

An instrumented drop weight impact test was used to study the effect of thermal degradation on the impact properties of PVC compounds. The impact resistance of the aged compounds related well with their weight loss and hence, with thermal degradation. Each compound showed a specific weight loss percentage that correlated with a 50% loss in its impact properties (failure point), irrespective of the aging temperature. The results were also used to estimate a thermal index (TI) of each compound in a rapid and reliable way.     

Loss of nitrogen from urea applied to rainfed wheat in varying rainfall zones in northern Syria

Fertilizer-applied Nitrogen (N) may be lost from the soil by various mechanisms, i.e., runoff, leaching, denitrification, and volatilization. The latter process is of primary concern in calcareous soils of arid and semi-arid regions, especially when urea is used. In this field study from northern Syria, urea alone, urea with either an incorporated urease inhibitor, phenylphosphorodiamidate, or an experimental bran-wax coating were evaluated on wheat for two cropping seasons at two experimental stations with varying average seasonal rainfall (340 mm, 270 mm). Loss of N was assessed with ¹⁵N by mass balance, i.e., the amount of N applied minus the crop N uptake and N remaining in the soil. Crop yields and N uptake were related to seasonal rainfall. Losses of N, apparently as volatilized NH₃, were relatively low at both sites, i.e., 11–18%. However, compared to the unmodified urea, neither the incorporated urease inhibitor nor the bran-wax coating had any effect on yields, N uptake or N loss. While urea hydrolysis is normally rapid, it may be delayed by dry conditions at the soil surface; similarly, unusually cold periods may delay nitrification following hydrolysis. Thus, under the cool-season conditions of rainfed cropping in the Middle East, efficient use of urea is not likely to be achieved by modification of the urea but by conventional management practices that ensure pre-plant soil incorporation or topdressing during early spring rains.     

The Innate Immune Glycoprotein Lactoferrin Represses the Helicobacter pylori cag Type IV Secretion System

Chronic infection with Helicobacter pylori increases risk of gastric diseases including gastric cancer. Despite development of a robust immune response, H. pylori persists in the gastric niche. Progression of gastric inflammation to serious disease outcomes is associated with infection with H. pylori strains which encode the cag Type IV Secretion System (cag T4SS). The cag T4SS is responsible for translocating the oncogenic protein CagA into host cells and inducing pro-inflammatory and carcinogenic signaling cascades. Our previous work demonstrated that nutrient iron modulates the activity of the T4SS and biogenesis of T4SS pili. In response to H. pylori infection, the host produces a variety of antimicrobial molecules, including the iron-binding glycoprotein, lactoferrin. Our work shows that apo-lactoferrin exerts antimicrobial activity against H. pylori under iron-limited conditions, while holo-lactoferrin enhances bacterial growth. Culturing H. pylori in the presence of holo-lactoferrin prior to co-culture with gastric epithelial cells, results in repression of the cag T4SS activity. Concomitantly, a decrease in biogenesis of cag T4SS pili at the host-pathogen interface was observed under these culture conditions by high-resolution electron microscopy analyses. Taken together, these results indicate that acquisition of alternate sources of nutrient iron plays a role in regulating the pro-inflammatory activity of a bacterial secretion system and present novel therapeutic targets for the treatment of H. pylori-related disease.     

Metallocene QACs: The Incorporation of Ferrocene Moieties into monoQAC and bisQAC Structures

Inspired by the incorporation of metallocene functionalities into a variety of bioactive structures, particularly antimicrobial peptides, we endeavored to broaden the structural variety of quaternary ammonium compounds (QACs) by the incorporation of the ferrocene moiety. Accordingly, 23 ferrocene-containing mono- and bisQACs were prepared in high yields and tested for activity against a variety of bacteria, including Gram-negative strains and a panel of clinically isolated MRSA strains. Ferrocene QACs were shown to be effective antiseptics with some displaying single-digit micromolar activity against all bacteria tested, demonstrating yet another step in the expansion of structural variety of antiseptic QACs.     

Effects of Al:Si and (Al + Na):Si ratios on the properties of the international simple glass,part II: Structure

High-alumina containing high-level waste (HLW) will be vitrified at the Waste Treatment Plant at the Hanford Site. The resulting glasses, high in alumina, will have distinct composition-structure-property (C-S-P) relationships compared to previously studied HLW glasses. These C-S-P relationships determine the processability and product durability of glasses and therefore must be understood. The main purpose of this study is to understand the detailed structural changes caused by Al:Si and (Al + Na):Si substitutions in a simplified nuclear waste model glass (ISG, international simple glass) by combining experimental structural characterizations and molecular dynamics (MD) simulations. The structures of these two series of glasses were characterized by neutron total scattering and ²⁷Al, ²³Na, ²⁹Si, and ¹¹B solid-state nuclear magnetic resonance (NMR) spectroscopy. Additionally, MD simulations were used to generate atomistic structural models of the borosilicate glasses and simulation results were validated by the experimental structural data. Short-range (eg, bond distance, coordination number, etc) and medium-range (eg, oxygen speciation, network connectivity, polyhedral linkages) structural features of the borosilicate glasses were systematically investigated as a function of the degree of substitution. The results show that bond distance and coordination number of the cation-oxygen pairs are relatively insensitive to Al:Si and (Al + Na):Si substitutions with the exception of the B-O pair. Additionally, the Al:Si substitution results in an increase in tri-bridging oxygen species, whereas (Al + Na):Si substitution creates nonbridging oxygen species. Charge compensator preferences were found for Si-[NBO] (Na⁺), ^[3]B-[NBO] (Na⁺), ^[4]B (mostly Ca²⁺), ^[4]Al (nearly equally split Na⁺ and Ca²⁺), and ^[6]Zr (mostly Ca²⁺). The network former-BO-network former linkages preferences were also tabulated; Si-O-Al and Al-O-Al were preferred at the expense of lower Si-O-^[3]B and ^[3]B-O-^[3]B linkages. These results provide insights on the structural origins of property changes such as glass-transition temperature caused by the substitutions, providing a basis for future improvements of theoretical and computer simulation models.