The effect of red blood cell orientation on the electrical impedance of pulsatile blood with implications for impedance cardiography

Impedance cardiography is an application of bioimpedance analysis primarily used in a research setting to determine cardiac output. It is a non invasive technique that measures the change in the impedance of the thorax which is attributed to the ejection of a volume of blood from the heart. The cardiac output is calculated from the measured impedance using the parallel conductor theory and a constant value for the resistivity of blood. However, the resistivity of blood has been shown to be velocity dependent due to changes in the orientation of red blood cells induced by changing shear forces during flow. The overall goal of this thesis was to study the effect that flow deviations have on the electrical impedance of blood, both experimentally and theoretically, and to apply the results to a clinical setting. The resistivity of stationary blood is isotropic as the red blood cells are randomly orientated due to Brownian motion. In the case of blood flowing through rigid tubes, the resistivity is anisotropic due to the biconcave discoidal shape and orientation of the cells. The generation of shear forces across the width of the tube during flow causes the cells to align with the minimal cross sectional area facing the direction of flow. This is in order to minimise the shear stress experienced by the cells. This in turn results in a larger cross sectional area of plasma and a reduction in the resistivity of the blood as the flow increases. Understanding the contribution of this effect on the thoracic impedance change is a vital step in achieving clinical acceptance of impedance cardiography. Published literature investigates the resistivity variations for constant blood flow. In this case, the shear forces are constant and the impedance remains constant during flow at a magnitude which is less than that for stationary blood. The research presented in this thesis, however, investigates the variations in resistivity of blood during pulsataile flow through rigid tubes and the relationship between impedance, velocity and acceleration. Using rigid tubes isolates the impedance change to variations associated with changes in cell orientation only. The implications of red blood cell orientation changes for clinical impedance cardiography were also explored. This was achieved through measurement and analysis of the experimental impedance of pulsatile blood flowing through rigid tubes in a mock circulatory system. A novel theoretical model including cell orientation dynamics was developed for the impedance of pulsatile blood through rigid tubes. The impedance of flowing blood was theoretically calculated using analytical methods for flow through straight tubes and the numerical Lattice Boltzmann method for flow through complex geometries such as aortic valve stenosis. The result of the analytical theoretical model was compared to the experimental impedance measurements through rigid tubes. The impedance calculated for flow through a stenosis using the Lattice Boltzmann method provides results for comparison with impedance cardiography measurements collected as part of a pilot clinical trial to assess the suitability of using bioimpedance techniques to assess the presence of aortic stenosis. The experimental and theoretical impedance of blood was shown to inversely follow the blood velocity during pulsatile flow with a correlation of -0.72 and -0.74 respectively. The results for both the experimental and theoretical investigations demonstrate that the acceleration of the blood is an important factor in determining the impedance, in addition to the velocity. During acceleration, the relationship between impedance and velocity is linear (r2 = 0.98, experimental and r2 = 0.94, theoretical). The relationship between the impedance and velocity during the deceleration phase is characterised by a time decay constant, ô , ranging from 10 to 50 s. The high level of agreement between the experimental and theoretically modelled impedance demonstrates the accuracy of the model developed here. An increase in the haematocrit of the blood resulted in an increase in the magnitude of the impedance change due to changes in the orientation of red blood cells. The time decay constant was shown to decrease linearly with the haematocrit for both experimental and theoretical results, although the slope of this decrease was larger in the experimental case. The radius of the tube influences the experimental and theoretical impedance given the same velocity of flow. However, when the velocity was divided by the radius of the tube (labelled the reduced average velocity) the impedance response was the same for two experimental tubes with equivalent reduced average velocity but with different radii. The temperature of the blood was also shown to affect the impedance with the impedance decreasing as the temperature increased. These results are the first published for the impedance of pulsatile blood. The experimental impedance change measured orthogonal to the direction of flow is in the opposite direction to that measured in the direction of flow. These results indicate that the impedance of blood flowing through rigid cylindrical tubes is axisymmetric along the radius. This has not previously been verified experimentally. Time frequency analysis of the experimental results demonstrated that the measured impedance contains the same frequency components occuring at the same time point in the cycle as the velocity signal contains. This suggests that the impedance contains many of the fluctuations of the velocity signal. Application of a theoretical steady flow model to pulsatile flow presented here has verified that the steady flow model is not adequate in calculating the impedance of pulsatile blood flow. The success of the new theoretical model over the steady flow model demonstrates that the velocity profile is important in determining the impedance of pulsatile blood. The clinical application of the impedance of blood flow through a stenosis was theoretically modelled using the Lattice Boltzman method (LBM) for fluid flow through complex geometeries. The impedance of blood exiting a narrow orifice was calculated for varying degrees of stenosis. Clincial impedance cardiography measurements were also recorded for both aortic valvular stenosis patients (n = 4) and control subjects (n = 4) with structurally normal hearts. This pilot trial was used to corroborate the results of the LBM. Results from both investigations showed that the decay time constant for impedance has potential in the assessment of aortic valve stenosis. In the theoretically modelled case (LBM results), the decay time constant increased with an increase in the degree of stenosis. The clinical results also showed a statistically significant difference in time decay constant between control and test subjects (P = 0.03). The time decay constant calculated for test subjects (ô = 180 - 250 s) is consistently larger than that determined for control subjects (ô = 50 - 130 s). This difference is thought to be due to difference in the orientation response of the cells as blood flows through the stenosis. Such a non-invasive technique using the time decay constant for screening of aortic stenosis provides additional information to that currently given by impedance cardiography techniques and improves the value of the device to practitioners. However, the results still need to be verified in a larger study. While impedance cardiography has not been widely adopted clinically, it is research such as this that will enable future acceptance of the method.

Extreme ultraviolet (EUV) degradation of poly(olefin sulfone)s : towards applications as EUV photoresists

Poly(olefin sulfone)s, formed by the reaction of sulfur dioxide (SO2) and an olefin, are known to be highly susceptible to degradation by radiation and thus have been identified as candidate materials for chain scission-based extreme ultraviolet lithography (EUVL) resist materials. In order to investigate this further, the synthesis and characterisation of two poly(olefin sulfone)s namely poly(1-pentene sulfone) (PPS) and poly(2-methyl-1-pentene sulfone) (PMPS), was achieved and the two materials were evaluated for possible chain scission EUVL resist applications. It was found that both materials possess high sensitivities to EUV photons; however; the rates of outgassing were extremely high. The only observed degradation products were found to be SO2 and the respective olefin suggesting that depolymerisation takes place under irradiation in a vacuum environment. In addition to depolymerisation, a concurrent conversion of SO2 moieties to a sulfide phase was observed using XPS.

Microscale study of electrical characteristics of epoxy-multiwall carbon nanotube nanocomposites

Epoxy-multiwall carbon nanotube nanocomposite thin films were prepared by spin casting. High power air plasma was used to preferentially etch a coating of epoxy and expose the underlying carbon nanotube network. Scanning electron microscopy (SEM) examination revealed well distributed and spatially connected carbon nanotube network in both the longitudinal direction (plasma etched surface) and traverse direction (through-thickness fractured surface). Topographical examination and conductive mode imaging of the plasma etched surface using atomic force microscope (AFM) in the contact mode enabled direct imaging of topography and current maps of the embedded carbon nanotube network. Bundles consisting of at least three single carbon nanotubes form part of the percolating network observed under high resolution current maps. Predominantly non-ohmic response is obtained in this study; behaviour attributed to less than effective polymer material removal when using air plasma etching.

Increased charge transfer of Poly (ethylene oxide) based electrolyte by addition of small molecule and its application in dye-sensitized solar cells

A Poly (ethylene oxide) based polymer electrolyte impregnated with 2-Mercapto benzimidazole was comprehensively characterized by XRD, UV–visible spectroscopy, FTIR as well as electrochemical impedance spectroscopy. It was found that the crystallization of PEO was dramatically reduced and the ionic conductivity of the electrolyte was increased 4.5 fold by addition of 2-Mercapto benzimidazole. UV–visible and FTIR spectroscopes indicated the formation of charge transfer complex between 2-Mercapto benzimidazole and iodine of the electrolyte. Dye-sensitized solar cells with the polymer electrolytes were assembled. It was found that both the photocurrent density and photovoltage were enhanced with respect to the DSC without 2-Mercapto benzimidazole, leading to a 60% increase of the performance of the cell.

Effect of Coulomb blockade, gold resistance, and thermal expansion on the electrical resistance of ultrathin gold films

Controlling the electrical resistance of granular thin films is of great importance for many applications, yet a full understanding of electron transport in such films remains a major challenge. We have studied experimentally and by model calculations the temperature dependence of the electrical resistance of ultrathin gold films at temperatures between 2 K and 300 K. Using sputter deposition, the film morphology was varied from a discontinuous film of weakly coupled meandering islands to a continuous film of strongly coupled coalesced islands. In the weak-coupling regime, we compare the regular island array model, the cotunneling model, and the conduction percolation model with our experimental data. We show that the tunnel barriers and the Coulomb blockade energies are important at low temperatures and that the thermal expansion of the substrate and the island resistance affect the resistance at high temperatures. At low temperatures our experimental data show evidence for a transition from electron cotunneling to sequential tunneling but the data can also be interpreted in terms of conduction percolation. The resistivity and temperature coefficient of resistance of the meandering gold islands are found to resemble those of gold nanowires. We derive a simple expression for the temperature at which the resistance changes from non-metal-like behavior into metal-like behavior. In the case of strong island coupling, the total resistance is solely determined by the Ohmic island resistance.

Structural, optical and electrical properties of Al-doped ZnO transparent conducting oxide for solar cell applications

Al-doped zinc oxide (AZO) thin films are deposited onto glass substrates using radio-frequency reactive magnetron sputtering and the improvements in their physical properties by post-synthesis thermal treatment are reported. X-ray diffraction spectra show that the structure of films can be controlled by adjusting the annealing temperatures, with the best crystallinity obtained at 400°C under a nitrogen atmosphere. These films exhibit improved quality and better optical transmittance as indicated by the UV-Vis spectra. Furthermore, the sheet resistivity is found to decrease from 1.87 × 10-3 to 5.63 × 10-4Ω⋅cm and the carrier mobility increases from 6.47 to 13.43 cm2 ⋅ V-1 ⋅ s-1 at the optimal annealing temperature. Our results demonstrate a simple yet effective way in controlling the structural, optical and electrical properties of AZO thin films, which is important for solar cell applications.

Improved energy harvesting capability of poly(vinylidene fluoride) films modified by reduced graphene oxide

Piezoelectric energy harvesters can be used to convert ambient energy into electrical energy and power small autonomous devices. In recent years, massive effort has been made to improve the energy harvesting ability in piezoelectric materials. In this study, reduced graphene oxide was added into poly(vinylidene fluoride) to fabricate the piezoelectric nanocomposite films. Open-circuit voltage and electrical power harvesting experiments showed remarkable enhancement in the piezoelectricity of the fabricated poly(vinylidene fluoride)/reduced graphene oxide nanocomposite, especially at an optimal reduced graphene oxide content of 0.05 wt%. Compared to pristine poly(vinylidene fluoride) films, the open-circuit voltage, the density of harvested power of alternating current, and direct current of the poly(vinylidene fluoride)/reduced graphene oxide nanocomposite films increased by 105%, 153%, and 233%, respectively, indicating a great potential for a broad range of applications.

Electrical characteristics of lateral heterostructure organic field-effect bipolar transistors

We describe and discuss the unique electrical characteristics of an organic field-effect transistor in which the active layer consists of a type II lateral heterojunction located approximately midway between the source and drain. The two active semiconductors on either side of the junction transport only one carrier type each, with the other becoming trapped, which leads to devices that operate in only the steady state when there is balanced electron and hole injections from the drain and source. We describe the unique transfer characteristics of such devices in two material systems.

Thermal conductivity of configurable two-dimensional carbon nanotube architecture and strain modulation

We reported the thermal conductivity of the two-dimensional carbon nanotube (CNT)-based architecture, which can be constructed through welding of single-wall CNTs by electron beam. Using large-scale nonequilibrium molecular dynamics simulations, the thermal conductivity is found to vary with different junction types due to their different phonon scatterings at the junction. The strong length and strain dependence of the thermal conductivity suggests an effective avenue to tune the thermal transport properties of the CNT-based architecture, benefiting the design of nanoscale thermal rectifiers or phonon engineering.

Preparation and characterization of poly(lactic-co-glycolic acid) microparticles containing DNA molecules encoding a malaria vaccine candidate

Background A novel ultrasonic atomization approach for the formulation of biodegradable poly(lactic-co-glycolic acid) (PLGA) microparticles of a malaria DNA vaccine is presented. A 40 kHz ultrasonic atomization device was used to create the microparticles from a feedstock containing 5 volumes of 0.5% w/v PLGA in acetone and 1 volume of condensed DNA which was fed at a flow rate of 18ml h-1. The plasmid DNA vectors encoding a malaria protein were condensed with a cationic polymer before atomization. Results High levels of gene expression in vitro were observed in COS-7 cells transfected with condensed DNA at a nitrogen to phosphate (N/P) ratio of 10. At this N/P ratio, the condensed DNA exhibited a monodispersed nanoparticle size (Z-average diameter of 60.8 nm) and a highly positive zeta potential of 38.8mV. The microparticle formulations of malaria DNA vaccine were quality assessed and it was shown that themicroparticles displayed high encapsulation efficiencies between 82-96% and a narrow size distribution in the range of 0.8-1.9 μm. In vitro release profile revealed that approximately 82% of the DNA was released within 30 days via a predominantly diffusion controlledmass transfer system. Conclusions This ultrasonic atomization technique showed excellent particle size reproducibility and displayed potential as an industrially viable approach for the formulation of controlled release particles.

Nitrogen-doped graphene films from chemical vapor deposition of pyridine: Influence of process parameters on the electrical and optical properties

Graphene films were produced by chemical vapor deposition (CVD) of pyridine on copper substrates. Pyridine-CVD is expected to lead to doped graphene by the insertion of nitrogen atoms in the growing sp2 carbon lattice, possibly improving the properties of graphene as a transparent conductive film. We here report on the influence that the CVD parameters (i.e., temperature and gas flow) have on the morphology, transmittance, and electrical conductivity of the graphene films grown with pyridine. A temperature range between 930 and 1070 °C was explored and the results were compared to those of pristine graphene grown by ethanol-CVD under the same process conditions. The films were characterized by atomic force microscopy, Raman and X-ray photoemission spectroscopy. The optical transmittance and electrical conductivity of the films were measured to evaluate their performance as transparent conductive electrodes. Graphene films grown by pyridine reached an electrical conductivity of 14.3 × 105 S/m. Such a high conductivity seems to be associated with the electronic doping induced by substitutional nitrogen atoms. In particular, at 930 °C the nitrogen/carbon ratio of pyridine-grown graphene reaches 3%, and its electrical conductivity is 40% higher than that of pristine graphene grown from ethanol-CVD.

Growth and attachment of Thiobacillus ferrooxidans during sulfide mineral leaching

The growth of Thiobacillus ferrooxidans, their attachment to sulfide minerals and detachment during bacterial leaching are discussed in this paper. Growth of the bacteria has been measured by cell count of the supernatants of the mineral suspensions while attachment to minerals and detachment were measured by periodic protein estimations for both the solid and liquid phases, Even in the absence of the nutrients, bacterial growth occurs and increases the available cell population during leaching; such growth was greater in sphalerite suspensions than in galena suspensions, The bacterial attachment studies suggest that more cells are attached onto galena mineral surface than to sphalerite surface. The mechanisms of bacterial attachment and detachment are discussed.

Photocatalytic and Thermal Degradation of Poly(methyl methacrylate), Poly(butyl acrylate), and Their Copolymers

The photocatalytic and thermal degradations of poly(methyl methacrylate), poly(butyl acrylate), and their copolymers of different compositions were studied. The photocatalytic degradation was investigated in o-dichlorobenzene in the presence of two different catalysts, namely, Degussa P-25 and combustion synthesized nanotitania (CSN-TiO2). The samples were analyzed by using gel permeation chromatography (GPC) to obtain the molecular weight distributions (MWDs) as a function of reaction time. Experimental data indicated that the photodegradation of these polymers occurs by both random and chain end scission. A continuous distribution kinetic model was used to determine the degradation rate coefficients by fitting the experimental data with the model. Both the random and specific rate coefficients of the copolymers decreased with increasing percentage of butyl acrylate (BA). Thermal degradation of the copolymers was investigated by thermo-gravimetry. The normalized weight loss profiles for the copolymers showed that the thermal stability of the copolymers increased with mole percentage of BA in the copolymer (PMMABA). The Czawa method was used to determine the activation energies at different conversions. At low acrylate content in the copolymer, the activation energy depends on conversion, indicating multiple degradation mechanisms. At high acrylate content in the copolymer, the activation energy is independent of conversion, indicating degradation by a one-step mechanism.

Adsorption and Desorption Kinetics of Anionic Dyes on Doped Polyaniline

In this study, we report an approach for the adsorption and desorption of anionic (sulfonated) dyes from aqueous solution by doped polyaniline. In this study, we have synthesized PANI with two dopants, namely, p-toluenesulfonic acid (PTSA) and camphorsulfonic acid (CSA), and used these to adsorb various dyes. It was found that the doped PANI selectively adsorbs anionic dyes and does not adsorb cationic dyes. The adsorption of anionic dyes causes the variation in electrical conductivity of PANI, indicating its potential as a conductometric sensor for these dyes at very low concentration. The adsorbed dyes were desorbed from the polymer by using a basic aqueous solution. The adsorption and desorption kinetics of the dye in the presence of doped PANI were also determined.

Thermal conductivity of a new carbon nanotube analog: The diamond nanothread

Based on the non-equilibrium molecular dynamics simulations, we have studied the thermal conductivities of a novel ultra-thin one-dimensional carbon nanomaterial - diamond nanothread (DNT). Unlike single-wall carbon nanotube (CNT), the existence of the Stone-Wales transformations in DNT endows it with richer thermal transport characteristics. There is a transition from wave-dominated to particle-dominated transport region, which depends on the length of poly-benzene rings. However, independent of the transport region, strong length dependence in thermal conductivity is observed in DNTs with different lengths of poly-benzene ring. The distinctive SW characteristic in DNT provides more degrees of freedom to tune the thermal conductivity not found in the homogeneous structure of CNT. Therefore, DNT is an ideal platform to investigate various thermal transport mechanisms at the nanoscale. Its high tunability raises the potential to design DNTs for different applications, such as thermal connection and temperature management.