A facile spin-cast route for cation exchange of multilayer perpendicularly-aligned nanorod assemblies

A facile spin cast route was developed to convert perpendicularly aligned nanorod assemblies of cadmium chalcogenides into their silver and copper analogues. The assemblies are rapidly cation exchanged without affecting either the individual rod dimensions or collective superlattice order extending over several multilayers.     

Complex Interactions among Sheep,Insects, Grass,and Fungi in a Simple New Zealand Grazing System

Epichloë fungi (Ascomycota) live within aboveground tissues of grasses and can have important implications for natural and managed ecosystems through production of alkaloids. Nonetheless, vertebrate herbivores may possess traits, like oral secretions, that mitigate effects of alkaloids. We tested if sheep saliva mitigates effects of Epichloë alkaloids on a beetle pest of perennial ryegrass (Lolium perenne L.) in a New Zealand pasture setting. Plants with one of several fungal isolates were clipped with scissors, grazed by sheep, or clipped with sheep saliva applied to cut ends of stems. We then assessed feeding damage by Argentine stem weevils on blade segments collected from experimental plants. We found that clipping plants induced synthesis of an alkaloid that reduces feeding by beetles and that sheep saliva mitigates this effect. Unexpectedly, the alkaloid (perloline) that explains variation in beetle feeding is one produced not by the endophyte, but rather by the plant. Yet, these effects depended upon fungal isolate. Such indirect, complex interactions may be much more common in both managed and natural grassland systems than typically thought and could have implications for managing grazing systems.     

Investigation of the temperature homogeneity of die melt flows in polymer extrusion

Polymer extrusion is fundamental to the processing of polymeric materials and melt flow temperature homogeneity is a major factor which influences product quality. Undesirable thermal conditions can cause problems such as melt degradation, dimensional instability, weaknesses in mechanical/optical/geometrical properties, and so forth. It has been revealed that melt temperature varies with time and with radial position across the die. However, the majority of polymer processes use only single‐point techniques whose thermal measurements are limited to the single point at which they are fixed. Therefore, it is impossible for such techniques to determine thermal homogeneity across the melt flow. In this work, an extensive investigation was carried out into melt flow thermal behavior of the output of a single extruder with different polymers and screw geometries over a wide range of processing conditions. Melt temperature profiles of the process output were observed using a thermocouple mesh placed in the flow and results confirmed that the melt flow thermal behavior is different at different radial positions. The uniformity of temperature across the melt flow deteriorated considerably with increase in screw rotational speed while it was also shown to be dependent on process settings, screw geometry, and material properties. Moreover, it appears that the effects of the material, machine, and process settings on the quantity and quality of the process output are heavily coupled with each other and this may cause the process to be difficult to predict and variable in nature. POLYM. ENG. SCI., 54:2430–2440, 2014. © 2013 Society of Plastics Engineers     

Improved zein films using polyethylenemaleic anhydride

The effect on the physical properties and solubility of corn protein (zein) films was studied after reaction of zein with polyethylenemaleic anhydride (PEMA). Reactions were carried out in dimethylformamide (DMF) solution where the concentration of PEMA was varied between 0 and 6%. After reaction at room temperature, cast films were prepared, and the physical and solubility properties were determined. Incorporating more than 2% PEMA provided films with increased tensile strength and elongation. Incorporating 6% PEMA provided films with higher tensile strength (32–42 MPa) and improved solvent resistance (100–21% solubility) relative to control. If the films were heated in an oven, the film's solubility decreased further. Solution rheology experiments demonstrated that the zein and PEMA formed a cross‐linked gel with time in DMF. Dynamic mechanical analysis experiments have shown that the PEMA‐modified zein films undergo a dramatic loss in modulus on reaching 116°C, whereas the control experiences this loss at 98°C. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40122.     

Assessing the Antimicrobial Activity of Polyisoprene Based Surfaces

There has been an intense research effort in the last decades in the field of biofouling prevention as it concerns many aspects of everyday life and causes problems to devices, the environment, and human health. Many different antifouling and antimicrobial materials have been developed to struggle against bacteria and other micro- and macro-organism attachment to different surfaces. However the “miracle solution” has still to be found. The research presented here concerns the synthesis of bio-based polymeric materials and the biological tests that showed their antifouling and, at the same time, antibacterial activity. The raw material used for the coating synthesis was natural rubber. The polyisoprene chains were fragmented to obtain oligomers, which had reactive chemical groups at their chain ends, therefore they could be modified to insert polymerizable and biocidal groups. Films were obtained by radical photopolymerization of the natural rubber derived oligomers and their structure was altered, in order to understand the mechanism of attachment inhibition and to increase the efficiency of the anti-biofouling action. The adhesion of three species of pathogenic bacteria and six strains of marine bacteria was studied. The coatings were able to inhibit bacterial attachment by contact, as it was verified that no detectable leaching of toxic molecules occurred.     

Tailoring Encodable Lanthanide‐Binding Tags as MRI Contrast Agents

Lanthanide‐binding tags (LBTs), peptide‐based coexpression tags with high affinity for lanthanide ions, have previously been applied as luminescent probes to provide phasing for structure determination in X‐ray crystallography and to provide restraints for structural refinement and distance information in NMR. The native affinity of LBTs for Gd³⁺ indicates their potential as the basis for engineering of peptide‐based MRI agents. However, the lanthanide coordination state that enhances luminescence and affords tightest binding would not be ideal for applications of LBTs as contrast agents, due to the exclusion of water from the inner coordination sphere. Herein, we use structurally defined LBTs as the starting point for re‐engineering the first coordination shell of the lanthanide ion to provide for high contrast through direct coordination of water to Gd³⁺ (resulting in the single LBT peptide, m‐sLBT). The effectiveness of LBTs as MRI contrast agents was examined in vitro through measurement of binding affinity and proton relaxivity. For imaging applications that require targeted observation, fusion to specific protein partners is desirable. However, a fusion protein comprising a concatenated double LBT (dLBT) as an N‐terminal tag for the model protein ubiquitin had reduced relaxivity compared with the free dLBT peptide. This limitation was overcome by the use of a construct based on the m‐sLBT sequence (q‐dLBT–ubiquitin). The structural basis for the enhanced contrast was examined by comparison of the X‐ray crystal structure of xq‐dLBT–ubiquitin (wherein two tryptophan residues are replaced with serine), to that of dLBT‐ubiquitin. The structure shows that the backbone conformational dynamics of the MRI variant may allow enhanced water exchange. This engineered LBT represents a first step in expanding the current base of specificity‐targeted agents available.     

Mutation of herpesvirus thymidine kinase to generate ganciclovir-specific kinases for use in cancer gene therapies

Understanding the functional and mechanistic properties of themulti-substrate herpes simplex virus type-1 thymidine kinase(HSV-1 TK) remains critical to defining its role as a majorpharmacological target in herpesvirus and gene therapies forcancer. An inherent limitation of the activity of HSV-TK isthe >70-fold difference in the K_ms for phosphorylation ofthymidine over the pro-drug ganciclovir (GCV). To engineer anHSV-1 TK isoform that is specific for GCV as the preferred substrate,16 site-specific mutants were generated. The mutations wereconcentrated at conserved residues involved in nucleoside basebinding, Gln125 and near sites 3 and 4 involved in catalysisand substrate binding. The substrate preferences of each mutantenzyme were compared with wild-type HSV-1 TK. One mutant, termedQ7530 TK, had a lower K_m for GCV than thymidine. Expressionof the Q7530 TK in tumor cells indicated comparable metabolismto and improved sensitivity to GCV over wild-type HSV-1 TK,with minimal thymidine phosphorylation activity. A molecularmodeling simulation of the different HSV-1 TK active-sites wasdone for GCV and thymidine binding. It was concluded that mutationsat Gln125 and near site 4, especially at Ala168, were responsiblefor loss of deoxypyrimidine substrate binding.     

Using CFD to predict the behavior of power law fluids near axial-flow impellers operating in the transitional flow regime

A computational fluid dynamics (CFD) model of flow in a mixing tank with a single axial-flow impeller was developed with the Fluent^TM software. The model consists of an unstructured hexagonal mesh (158,000 total cells), dense in the region from the surface of the impeller. The flow was modeled as laminar and a multiple reference frame approach was used to solve the discretized equations of motion in one-quarter of a baffled tank. A solution of 0.1% Carbopol in water, a shear-thinning fluid, was found to be clear enough to measure impeller discharge angles using laser Doppler velocimetry. This is the first time that impeller discharge angles have been reported in the literature for a shear-thinning fluid with a hydrofoil impeller. Rheological measurements indicated that the Carbopol solution can be characterized by the power law (K=9,n=0.2) under the range of shear conditions (0.1- expected near the impeller in the mixing tank. The CFD model accurately predicted the dependence of power number and discharge angle on Reynolds number (as predicted by Metzner and Otto), for an A200 (pitched blade turbine or PBT) and an A315 (Hydrofoil) impeller operating in the transitional flow regime (Reynolds numbers: 25-400) with glycerin and 0.1% Carbopol solutions. Subsequently, the results of a systematic CFD study with power law fluids indicated that the power number and discharge angle of an axial-flow impeller in the transitional flow regime depends not only on the Reynolds number (as determined by Metzner and Otto's method) but also on the flow behavior index n. Consequently, an alternative to Metzner and Otto's method was pursued. The results of converged CFD simulations indicate that the near-impeller “average shear rate” increases not only with increasing RPM (as proposed by Metzner and Otto), but also with decreasing flow behavior index (n) and discharge angle in the transitional flow regime. Considering this result, an improved method of estimating the power number and discharge angle for power law fluids in the transitional flow regime is proposed.     

The Effects of Power Law Fluid Rheology on Coil Heat Transfer for Agitated Vessel in the Transitional Flow Regime

A CFD model of heat transfer from power‐law fluids to helical cooling coils in the transitional flow regime of a baffled tank mixed with a pitched blade turbine was developed with Fluent^TM. The model captured local temperature and velocity gradients. Simulations were run, varying Re, Pr, K and n. The results indicate that a Sieder‐Tate type correlation, with the exponent on and the coefficient in front of the Reynolds number being a function of n, is recommended for estimating ho. Also, a new two coil bank design was found to be more efficient when 450 < Re < 650.