MICROFLUIDIC ASSAY PERFORMANCE ENHANCEMENT USING POROUS VOLUMETRIC DETECTION ELEMENTS FOR IMPEDEMETRIC AND OPTICAL SENSING

Microfluidic technologies have great potential to help create automated, cost-effective, portable devices for rapid point of care (POC) diagnostics in diverse patient settings. Unfortunately commercialization is currently constrained by the materials, reagents, and instrumentation required and detection element performance. While most microfluidic studies utilize planar detection elements, this dissertation demonstrates the utility of porous volumetric detection elements to improve detection sensitivity and reduce assay times. Impedemetric immunoassays were performed utilizing silver enhanced gold nanoparticle immunoconjugates (AuIgGs) and porous polymer monolith or silica bead bed detection elements within a thermoplastic microchannel. For a direct assay with 10 µm spaced electrodes the detection limit was 0.13 fM AuIgG with a 3 log dynamic range. The same assay was performed with electrode spacing of 15, 40, and 100 µm with no significant difference between configurations. For a sandwich assay the detection limit was10 ng/mL with a 4 log dynamic range. While most impedemetric assays rely on expensive high resolution electrodes to enhance planar senor performance, this study demonstrates the employment of porous volumetric detection elements to achieve similar performance using lower resolution electrodes and shorter incubation times. Optical immunoassays were performed using porous volumetric capture elements perfused with refractive index matching solutions to limit light scattering and enhance signal. First, fluorescence signal enhancement was demonstrated with a porous polymer monolith within a silica capillary. Next, transmission enhancement of a direct assay was demonstrated by infusing aqueous sucrose solutions through silica bead beds with captured silver enhanced AuIgGs yielding a detection limit of 0.1 ng/mL and a 5 log dynamic range. Finally, ex situ functionalized porous silica monolith segments were integrated into thermoplastic channels for a reflectance based sandwich assay yielding a detection limit of 1 ng/mL and a 5 log dynamic range. The simple techniques for optical signal enhancement and ex situ element integration enable development of sensitive, multiplexed microfluidic sensors. Collectively the demonstrated experiments validate the use of porous volumetric detection elements to enhance impedemetric and optical microfluidic assays. The techniques rely on commercial reagents, materials compatible with manufacturing, and measurement instrumentation adaptable to POC diagnostics.

Porous self-protonating spiropyran-based NIPAAm gels with improved reswelling kinetics

The final publication is available at Springer via http://dx.doi.org/[10.1007/s10853-015-9458-2]

Viability of irrigation by porous capsule method in arid and semi-arid regions.

This paper presents the results of four field experiments carried out with the objetive of evaluating the feaibility of irrigation by porous capsule method, from 1979 to 1983, at Bebedouro Experiment Station, EMBRAPA-CPATSA, Petrolina, PE, Brazil. The irrigation system consisted of fulcrum of cone shaped porous capsules, interconnected with conduit pipe and installed in the soil at equidistance and 0.10 m deep along contour lines. The hydrostatic pressures studies did not significantly influence the crop yield, but influenced, at 0.10 level, the daily water release from porous unit. The mean yields for watermelon (Citrullus vulgaris Shard), var. Charleston Gray, for muskmelon (Cucumis melo L.) var. Valenciano Amarelo, and for maize (Zea mays L.), var. Centralmex, estimated in ton/2,500 units/ha or in cobs/2,500 units/ha, were 28.5, 10 and 17,500, respectively. The water consumption for watermelon, musk melon and maize was, respectively, 60 mm, 60 mm and 100 mm in a deep sandy yellow-red latosol. The cost of the system was US$ 1.677,41/ha.

Thermodynamic calculations for the salt crystallisation damage in porous built heritage using PHREEQC

This work considers the crystallisation mechanisms of the most common and aggressive salts that generate stress in porous building stones as a result of changing ambient conditions. These mechanisms include the salt crystallisation that result from decreasing relative humidity and changes in temperature and, in hydrated salts, the dissolution of the lower hydrated form and the subsequent precipitation of the hydrated salt. We propose a new methodology for thermodynamic calculations using PHREEQC that includes these crystallisation mechanisms. This approach permits the calculation of the equilibrium relative humidity and the parameterization of the critical relative humidity and crystallisation pressures for the dissolution–precipitation transitions. The influence of other salts on the effectives of salt crystallisation and chemical weathering is also assessed. We review the sodium and magnesium sulphate and sodium chloride systems, in both single and multicomponent solutions, and they are compared to the sodium carbonate and calcium carbonate systems. The variation of crystallisation pressure, the formation of new minerals and the chemical dissolution by the presence of other salts is also evaluated. Results for hydrated salt systems show that high crystallisation pressures are possible as lower hydrated salts dissolve and more hydrated salts precipitate. High stresses may be also produced by decreasing temperature, although it requires that porous materials are wet for long periods of time. The presence of other salts changes the temperature and relative humidity of salt transitions that generates stress rather than reducing the pressure of crystallisation, if any salt has previously precipitated. Several practical conclusions derive from proposed methodology and provide conservators and architects with information on the potential weathering activity of soluble salts. Furthermore, the model calculations might be coupled with projections of future climate to give as improved understanding of the likely changes in the frequency of phase transitions in salts within porous stone.

In situ characterization of porous VPO catalysts with fibrous structure: Identifying the redox behavior and the stability of active sites

Two VPO materials with fibrillar morphology have been prepared by the aid of electrospinning technique. One is a VPO carbon-supported material (VCF200) with fibrous morphology and very high surface area that is stable under oxidizing conditions up to 350C. The other material is a bulk mixed VPO oxide (VPO500) with fibrous structure obtained after optimizing the calcination of the carbon support in VCF200. Despite it is a bulk oxide material, this material exhibits a high surface area (> 60 m2/g). The redox behavior of both samples was monitored by in situ Raman spectroscopy under oxidation/reduction cycles. For the dehydrated supported sample (VCF200), the pyrophosphate phase (VO)2P2O7 (Raman ~930 cm-1) is detected, which has been described as the active phase (see Figure (a) below). This phase is quite stable since it does not disappear upon subsequent oxidation/reduction cycles. Under reduction conditions at 125C, in consecutive cycles, additional Raman bands appear at ~1090 cm-1 that are characteristic of the αII-VOPO4 phase. On the other hand, the bulk phases show a reversible behavior under redox cycles (Figure (b)). Under reducing conditions, a Raman band appears at ~980 cm-1 (β-VPO phase), whereas under oxidation conditions some segregation to VOx oxides occurs. Nevertheless, this segregation is reversible and the β-VPO phase forms again under reducing conditions. Thus, these results demonstrate that the active VPO phases of these fibrous catalysts are quite stable, and that their structure is reversible under several redox cycles, which make them suitable as oxidation catalysts.

Synthesis of porous graphene/TiO2 by use of recycled graphite

Graphene-based nanomaterials are a kind of new technological materials with high interest for physicists, chemists and materials scientists. Graphene is a two-dimensional (2-D) sheet of carbon atoms in a hexagonal configuration with atoms bonded by sp2 bonds. These bonds and this electron configuration provides the extraordinary properties of graphene, such as very large surface area, a tunable band gap, high mechanical strength and high elasticity and thermal conductivity [1]. Graphene has also been investigated for preparation of composites with various semiconductors like TiO2, ZnO, CdS aiming at enhanced photocatalytic activity for their use for photochemical reaction as water splitting or CO2 to methanol conversion [2-3]. In this communication, the synthesis of porous graphene@TiO2 obtained from a powder graphite recycled, supplied by ECOPIBA, is presented. This graphite was exfoliated, using a nonionic surfactant (Triton X-100) and sonication. Titanium(IV) isopropoxide was used as TiO2 source. After removing the surfactant with a solution HCl/n-propanol, a porous solid is obtained with a specific area of 358 m2g-1. The solid was characterized by XRD, FTIR, XPS, EDX and TEM. Figure 1 shows the graphene 2D layer bonded with nanoparticles of TiO2. When a water suspension of this material is exposed with UV-vis radiation, water splitting reaction is carried out and H2/O2 bubbles are observed (Figure 2)

WATER TRANSPORT THROUGH POROUS MEDIA AND IN FLOW CHANNELS OF PROTON EXCHANGE MEMBRANE FUEL CELL

Proton exchange membrane (PEM) fuel cell has been known as a promising power source for different applications such as automotive, residential and stationary. During the operation of a PEM fuel cell, hydrogen is oxidized in anode and oxygen is reduced in the cathode to produce the intended power. Water and heat are inevitable byproducts of these reactions. The water produced in the cathode should be properly removed from inside the cell. Otherwise, it may block the path of reactants passing through the gas channels and/or gas diffusion layer (GDL). This deteriorates the performance of the cell and eventually can cease the operation of the cell. Water transport in PEM fuel cell has been the subject of this PhD study. Water transport on the surface of the GDL, through the gas flow channels, and through GDL has been studied in details. For water transport on the surface of the GDL, droplet detachment has been measured for different GDL conditions and for anode and cathode gas flow channels. Water transport through gas flow channels has been investigated by measuring the two-phase flow pressure drop along the gas flow channels. As accumulated liquid water within gas flow channels resists the gas flow, the pressure drop increases along the flow channels. The two-phase flow pressure drop can reveal useful information about the amount of liquid water accumulated within gas flow channels. Liquid water transport though GDL has also been investigated by measuring the liquid water breakthrough pressure for the region between the capillary fingering and the stable displacement on the drainage phase diagram. The breakthrough pressure has been measured for different variables such as GDL thickness, PTFE/Nafion content within the GDL, GDL compression, the inclusion of a micro-porous layer (MPL), and different water flow rates through the GDL. Prior to all these studies, GDL microstructural properties have been studied. GDL microstructural properties such as mean pore diameter, pore diameter distribution, and pore roundness distribution have been investigated by analyzing SEM images of GDL samples.

Meshfree Method for Prediction of Thermal Properties of Porous Ceramic Materials

In the presented thesis work, meshfree method with distance fields is applied to create a novel computational approach which enables inclusion of the realistic geometric models of the microstructure and liberates Finite Element Analysis(FEA) from thedependance on and limitations of meshing of fine microstructural feature such as splats and porosity.Manufacturing processes of ceramics produce materials with complex porosity microstructure.Geometry of pores, their size and location substantially affect macro scale physical properties of the material. Complex structure and geometry of the pores severely limit application of modern Finite Element Analysis methods because they require construction of spatial grids (meshes) that conform to the geometric shape of the structure. As a result, there are virtually no effective tools available for predicting overall mechanical and thermal properties of porous materials based on their microstructure. This thesis is a separate handling and controls of geometric and physical computational models that are seamlessly combined at solution run time. Using the proposedapproach we will determine the effective thermal conductivity tensor of real porous ceramic materials featuring both isotropic and anisotropic thermal properties. This work involved development and implementation of numerical algorithms, data structure, and software.

Effects of truck traffic on top-down fatigue cracking performance of flexible pavements using a new mechanics-based analysis framework

The mechanics-based analysis framework predicts top-down fatigue cracking initiation time in asphalt concrete pavements by utilising fracture mechanics and mixture morphology-based property. To reduce the level of complexity involved, traffic data were characterised and incorporated into the framework using the equivalent single axle load (ESAL) approach. There is a concern that this kind of simplistic traffic characterisation might result in erroneous performance predictions and pavement structural designs. This paper integrates axle load spectra and other traffic characterisation parameters into the mechanics-based analysis framework and studies the impact these traffic characterisation parameters have on predicted fatigue cracking performance. The traffic characterisation inputs studied are traffic growth rate, axle load spectra, lateral wheel wander and volume adjustment factors. For this purpose, a traffic integration approach which incorporates Monte Carlo simulation and representative traffic characterisation inputs was developed. The significance of these traffic characterisation parameters was established by evaluating a number of field pavement sections. It is evident from the results that all the traffic characterisation parameters except truck wheel wander have been observed to have significant influence on predicted top-down fatigue cracking performance.

Primary alkaline battery cathodes a three-scale model

A mathematical model for the galvanostatic discharge and recovery of porous, electrolytic manganese dioxide cathodes, similar to those found within primary alkaline batteries is presented. The phenomena associated with discharge are modeled over three distinct size scales, a cathodic (or macroscopic) scale, a porous manganese oxide particle (or microscopic) scale, and a manganese oxide crystal (or submicroscopic) scale. The physical and chemical coupling between these size scales is included in the model. In addition, the model explicitly accounts for the graphite phase within the cathode. The effects that manganese oxide particle size and proton diffusion have on cathodic discharge and the effects of intraparticle voids and microporous electrode structure are predicted using the model.

Flow of a micropolar fluid bounded by a stretching sheet

We consider boundary layer flow of a micropolar fluid driven by a porous stretching sheet. A similarity solution is defined, and numerical solutions using Runge-Kutta and quasilinearisation schemes are obtained. A perturbation analysis is also used to derive analytic solutions to first order in the perturbing parameter. The resulting closed form solutions involve relatively complex expressions, and the analysis is made more tractable by a combination of offline and online work using a computational algebra system (CAS). For this combined numerical and analytic approach, the perturbation analysis yields a number of benefits with regard to the numerical work. The existence of a closed form solution helps to discriminate between acceptable and spurious numerical solutions. Also, the expressions obtained from the perturbation work can provide an accurate description of the solution for ranges of parameters where the numerical approaches considered here prove computationally more difficult.

Managing knowledge in an outsourcing environment

What an organisation does versus what it out-sources to the market is a classic boundaries of the firm question that has previously been dominated by efficiency arguments. However, a knowledge-based view suggests these boundaries are integral to the ability of a firm to deploy existing knowledge stocks efficiently, as well as develop new knowledge through learning that will drive future competitiveness. Furthermore, the nature of these boundaries, in respect of their permeability is critical in understanding the likelihood of knowledge flowing into and out of the organisation. Using these concepts, we present a case study of Main Roads Western Australia to illustrate how these principles have allowed it to start rebuilding its internal capabilities through repositioning its operational boundaries and via ensuring their boundaries are highly porous as they move more major projects into alliance contracts.