Effects of electron-beam irradiation on chemical and antioxidation parameters of wild Macrolepiota procera dried samples

Mushrooms are very perishable foods due to their high susceptibility to moisture loss, changes in color and texture, or microbiological spoilage. Drying is considered as the most appropriate method to prevent these alterations, but it has some limitations, such as shrinkage, enzymatic and non-enzymatic browning reactions, and oxidation of lipids and vitamins. Irradiation might effectively attenuate the undesirable changes caused by drying process, ensuring also higher shelf-life of mushrooms and their decontamination [I]. In the present work, the combined effects of electron-beam irradiation (at 0, 0.5, 1 and 6 kGy doses) and storage time (at 0, 6 and 12 months) were evaluated and compared. Macrolepiota procera (Scop.) Singer wild samples were obtained in Tnis-os-Montes, in the Northeast of Portugal, and dried at 30 •c in an oven. Subsequently, the samples were divided in four groups: control (non-irradiated, 0 kGy); sample 1 (0.5 kGy); sample 2 (1 kGy) and sample 3 (6 kGy). The irradiation was performed at the lNCTInstitute of Nuclear Chemistry and Technology (lNCT), in Warsaw, Poland. Moisture, protein, fat, carbohydrates and ash were determined following standard procedures. Free sugars and tocopherols were determined by high performance liquid chromatography coupled to a refraction index detector (HPLC-RI) and a fluorescence detector, respectively; fatty acids were determined by gas-liquid chromatography with flame ionization detection (GC-FID). Antioxidant activity was evaluated in the methanolic extracts by in vitro assays measuring DPPH (1,1-diphenyl-2- picrylhydrazyl) radical scavenging activity, reducing power, inhibition of ~-carotene bleaching and inhibition oflipid peroxidation using thiobarbituric acid reactive substances (TBARS) assay. Total phenolics were also determined by the Folin-Ciocalteu assay. All the parameters showed a decrease tendency with storage time. Trehalose and y-tocopherol were preserved with 1 kGy dose. Electron-beam irradiation did not impart additional changes to most of the chemical and antioxidant parameters of M. procera dried samples. This is a very promising result, since electron-beam irradiation might attenuate most unwanted changes caused by drying, maintaining its long-term effectiveness.

Transmission electron tomography: quality assessment and enhancement for three-dimensional imaging of nanostructures

Nanotechnology has revolutionised humanity's capability in building microscopic systems by manipulating materials on a molecular and atomic scale. Nan-osystems are becoming increasingly smaller and more complex from the chemical perspective which increases the demand for microscopic characterisation techniques. Among others, transmission electron microscopy (TEM) is an indispensable tool that is increasingly used to study the structures of nanosystems down to the molecular and atomic scale. However, despite the effectivity of this tool, it can only provide 2-dimensional projection (shadow) images of the 3D structure, leaving the 3-dimensional information hidden which can lead to incomplete or erroneous characterization. One very promising inspection method is Electron Tomography (ET), which is rapidly becoming an important tool to explore the 3D nano-world. ET provides (sub-)nanometer resolution in all three dimensions of the sample under investigation. However, the fidelity of the ET tomogram that is achieved by current ET reconstruction procedures remains a major challenge. This thesis addresses the assessment and advancement of electron tomographic methods to enable high-fidelity three-dimensional investigations. A quality assessment investigation was conducted to provide a quality quantitative analysis of the main established ET reconstruction algorithms and to study the influence of the experimental conditions on the quality of the reconstructed ET tomogram. Regular shaped nanoparticles were used as a ground-truth for this study. It is concluded that the fidelity of the post-reconstruction quantitative analysis and segmentation is limited, mainly by the fidelity of the reconstructed ET tomogram. This motivates the development of an improved tomographic reconstruction process. In this thesis, a novel ET method was proposed, named dictionary learning electron tomography (DLET). DLET is based on the recent mathematical theorem of compressed sensing (CS) which employs the sparsity of ET tomograms to enable accurate reconstruction from undersampled (S)TEM tilt series. DLET learns the sparsifying transform (dictionary) in an adaptive way and reconstructs the tomogram simultaneously from highly undersampled tilt series. In this method, the sparsity is applied on overlapping image patches favouring local structures. Furthermore, the dictionary is adapted to the specific tomogram instance, thereby favouring better sparsity and consequently higher quality reconstructions. The reconstruction algorithm is based on an alternating procedure that learns the sparsifying dictionary and employs it to remove artifacts and noise in one step, and then restores the tomogram data in the other step. Simulation and real ET experiments of several morphologies are performed with a variety of setups. Reconstruction results validate its efficiency in both noiseless and noisy cases and show that it yields an improved reconstruction quality with fast convergence. The proposed method enables the recovery of high-fidelity information without the need to worry about what sparsifying transform to select or whether the images used strictly follow the pre-conditions of a certain transform (e.g. strictly piecewise constant for Total Variation minimisation). This can also avoid artifacts that can be introduced by specific sparsifying transforms (e.g. the staircase artifacts the may result when using Total Variation minimisation). Moreover, this thesis shows how reliable elementally sensitive tomography using EELS is possible with the aid of both appropriate use of Dual electron energy loss spectroscopy (DualEELS) and the DLET compressed sensing algorithm to make the best use of the limited data volume and signal to noise inherent in core-loss electron energy loss spectroscopy (EELS) from nanoparticles of an industrially important material. Taken together, the results presented in this thesis demonstrates how high-fidelity ET reconstructions can be achieved using a compressed sensing approach.

Effects of gamma and electron beam irradiation in the antioxidante potential of methanolic extracts and infusions of Arenaria Montana L

Irradiation is a methodology qualified for dry ingredients preservation or decontamination and can be performed using various radiation sources and energy levels in accordance with the objectives to be achieved [1]. Electron beam irradiation is used mainly for food products with low density, while gamma irradiation is mainly used for large volumes [2]. Arenaria Montana L. has a high antioxidant potential and richness in bioactive phytochemicals. It is used in Portuguese traditional medicine, acting therapeutically as an anti-inflammatory and diuretic plant [3]. The aim of this work was to evaluate the effects of gamma and electron beam irradiation at different doses (I and 10 kGy) in the antioxidant activity of A. montana. Free radicals scavenging activity, reducing power and lipid peroxidation inhibition properties of its methanolic extracts and infusions were evaluated. Through a global analysis, it was concluded that the antioxidant activity proved to be higher in methanolic extracts in comparison with the infusions, where it decreased with increasing irradiation dose regardless of the technology used (gamma or electron beam). For methanolic extracts, electron beam resulted in increased antioxidant activity while gamma irradiation caused a decrease in these extracts. Thus, the antioxidant potential is variable depending not only on the type of radiation and the dose applied, but also on the solvent used in the preparation of the extracts (methanol or water).

Analysis of β-tricalcium phosphate granules prepared with different formulations by nano-computed tomography and scanning electron microscopy

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High fat-fed diabetic mice present with profound alterations of the osteocyte network

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High On/Off ratio memristive switching of manganite/cuprate bilayer by interfacial magnetoelectricity

Memristive switching serves as the basis for a new generation of electronic devices. Memristors are two-terminal devices in which the current is turned on and off by redistributing point defects, e.g., vacancies, which is difficult to control. Memristors based on alternative mechanisms have been explored, but achieving both the high On/Off ratio and the low switching energy desirable for use in electronics remains a challenge. Here we report memristive switching in a La_(0.7)Ca_(0.3)MnO_(3)/PrBa_(2)Cu_(3)O_(7) bilayer with an On/Off ratio greater than 103 and demonstrate that the phenomenon originates from a new type of interfacial magnetoelectricity. Using results from firstprinciples calculations, we show that an external electric-field induces subtle displacements of the interfacial Mn ions, which switches on/off an interfacial magnetic “dead” layer, resulting in memristive behavior for spin-polarized electron transport across the bilayer. The interfacial nature of the switching entails low energy cost about of a tenth of atto Joule for write/erase a “bit”. Our results indicate new opportunities for manganite/cuprate systems and other transition-metal-oxide junctions in memristive applications.

Electron microprobe investigations of metamorphic reactions and mineral growth histories, Kwoiek area, British Columbia

The Kwoiek Area of British Columbia contains a pendant or screen of metamorphosed sedimentary and volcanic rocks almost entirely surrounded by a portion of the Coast Range Batholith, and intruded by several dozen stocks. The major metamorphic effects were produced by the quartz diorite batholithic rocks, with minor and later effects by the quartz diorite stocks. The sequence of important metamorphic reactions in the metasedimentary and metavolcanic rocks, ranging in grade from chlorite to sillimanite, is:

1. chlorite + carbonate + muscovite → epidote + biotite

2. chlorite + carbonate → actinolite + epidote

3. chlorite + muscovite → garnet + biotite

4. chlorite + epidote → garnet + hornblende

5. chlorite + muscovite → garnet + staurolite + biotite

6. chlorite + muscovite → aluminum silicate + biotite

7. muscovite + staurolite → garnet + aluminum silicate + biotite

8. staurolite → garnet + aluminum silicate

Continuous reactions, occurring between reactions 5 and 7, are:

A. chlorite + (high Ti) biotite + Al₂O₃ (from plagioclase?)→ garnet + staurolite + (low Ti) biotite + O₂

B. muscovite (phengitic) → garnet + staurolite +muscovite (less phengitic) + O₂ (?)

Detailed electron microprobe work on garnet, staurolite, biotite, and chlorite shows that:

(1) The garnet porphyroblasts are zoned according to a depletion model, called the Rayleigh depletion model, which assumes equilibrium between the edge of a growing garnet and the minerals which are unzoned, notably biotite, chlorite, and muscovite, but which assumes disequilibrium within the garnet.

(2) The staurolite porphyroblasts are also zoned, and from their zoning patterns reactions A, B, and 5 are documented. Progressive reduction of iron with increasing grade of metamorphism is also inferred from the staurolite zoning patterns.

(3) During a late period of falling temperature garnet continued to grow and the biotite and chlorite reequilibrated. The biotite, chlorite, and garnet edge compositions can vary from point to point in a given thin section, indicating that the volume of equilibrium at the final stage of metamorphism was only a few cubic microns.

(4) The horizon within the garnet that grew at maximum temperature can be identified. The Mg/Fe ratio of this horizon, if the garnet composition is a limiting composition in the Al₂O₃ - K₂O - FeO - MgO tetrahedron, increases systematically with increasing metamorphic grade. Biotite and chlorite compositions also show a general increase in Mg/Fe ratio with increasing metamorphic grade, but staurolite appears to show the reverse effect.

(5) The Mg/Fe ratio at the maximum temperature horizon of the garnet porphyroblasts is a function of its Mn content as evidenced from the study of five garnet-bearing rocks, collected from one outcrop area, with the same assemblage but with differing proportions of minerals.

An important implication of zoned minerals is that the effective composition of a system in a phase lies on the join between the homogeneous minerals (if there are two) and not within three-or- four-phase fields when a zoned mineral, such as garnet or staurolite, is present in the assemblage.

Study of the three aluminum silicates found in the Kwoiek Area showed that a constant pressure change in polymorphs from andalusite to kyanite to sillimanite took place with increasing temperature. This transition series is best explained by the metastable formation of andalusite.

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Social Mobility and Demand for Redistribution. A Comparative Analysis

The literature on preferences for redistribution has paid little attention to the effect of social mobility on the demand for redistribution, which is in contrast with the literature on class-voting, where studies on the effect of social mobility has been very common. Some works have addressed this issue but no systematic test of the hypotheses connecting social mobility and preferences has been done. In this paper we use the diagonal reference models to estimate the effect of origin and destination class on preferences for redistribution in a sample of European countries using data from the European Social Survey. Our findings indicate that social origin matters to a little extent to explain preferences, as newcomers tend to adopt the preferences of the destination class. Moreover, we have found only limited evidence supporting the acculturation hypothesis and not support for the status maximization hypothesis. Furthermore, the effect of social origin varies largely between countries. In a second step of the analysis we investigate what are the national factors explaining this variation. The empirical evidence we present leads to conclude that high rates of upward social mobility sharply reduce the effect of social origin on preferences for redistribution

Identical Location Transmission Electron Microscopy Imaging of Site-Selective Pt Nanocatalysts: Electrochemical Activation and Surface Disordering

We have employed identical location transmission electron microscopy (IL-TEM) to study changes in the shape and morphology of faceted Pt nanoparticles as a result of electrochemical cycling; a procedure typically employed for activating platinum surfaces. We find that the shape and morphology of the as-prepared hexagonal nanoparticles are rapidly degraded as a result of potential cycling up to +1.3 V. As few as 25 potential cycles are sufficient to cause significant degradation, and after about 500–1000 cycles the particles are dramatically degraded. We also see clear evidence of particle migration during potential cycling. These finding suggest that great care must be exercised in the use and study of shaped Pt nanoparticles (and related systems) as electrocatlysts, especially for the oxygen reduction reaction where high positive potentials are typically employed.

Evolution of surface properties of ornamental granitoids exposed to high temperatures

Granite submitted to high temperatures may lead to the loss of aesthetic values even before structural damage is caused. Thirteen granitoids were exposed to target temperatures, 200 °C, 400 °C, 600 °C, 800 °C and 1000 °C. Damage characterisation, including roughness, colour and oxidation of chromogen elements by means of X-ray photoelectron spectroscopy (XPS) was assessed. Altered granitoids are more resistant to structural failure but redden rapidly. Black mica-rich granitoids turn into yellow with a maximum at 800 °C. Alkali feldspar-rich granitoids redden progressively due to iron oxidation. Roughness varies progressively in mica-rich granitoids, while in mica-poor granitoids, an increase in roughness precedes catastrophic failure.

Post-CMOS compatible high-throughput fabrication of AIN-based piezoelectric microcantilevers

A post-complementary metal oxide semiconductor (CMOS) compatible microfabrication process of piezoelectric cantilevers has been developed. The fabrication process is suitable for standard silicon technology and provides low-cost and high-throughput manufacturing. This work reports design, fabrication and characterization of piezoelectric cantilevers based on aluminum nitride (AlN) thin films synthesized at room temperature. The proposed microcantilever system is a sandwich structure composed of chromium (Cr) electrodes and a sputtered AlN film. The key issue for cantilever fabrication is the growth at room temperature of the AlN layer by reactive sputtering, making possible the innovative compatibility of piezoelectric MEMS devices with CMOS circuits already processed. AlN and Cr have been etched by inductively coupled plasma (ICP) dry etching using a BCl3–Cl2–Ar plasma chemistry. As part of the novelty of the post-CMOS micromachining process presented here, a silicon Si (1 0 0) wafer has been used as substrate as well as the sacrificial layer used to release the microcantilevers. In order to achieve this, the Si surface underneath the structure has been wet etched using an HNA (hydrofluoric acid + nitric acid + acetic acid) based solution. X-ray diffraction (XRD) characterization indicated the high crystalline quality of the AlN film. An atomic force microscope (AFM) has been used to determine the Cr electrode surface roughness. The morphology of the fabricated devices has been studied by scanning electron microscope (SEM). The cantilevers have been piezoelectrically actuated and their out-of-plane vibration modes were detected by vibrometry.

IN-SITU ELECTRICAL, MECHANICAL AND ELECTROCHEMICAL CHARACTERIZATIONS OF ONE-DIMENSIONAL NANOSTRUCTURES

One-dimensional nanostructures initiated new aspects to the materials applications due to their superior properties compared to the bulk materials. Properties of nanostructures have been characterized by many techniques and used for various device applications. However, simultaneous correlation between the physical and structural properties of these nanomaterials has not been widely investigated. Therefore, it is necessary to perform in-situ study on the physical and structural properties of nanomaterials to understand their relation. In this work, we will use a unique instrument to perform real time atomic force microscopy (AFM) and scanning tunneling microscopy (STM) of nanomaterials inside a transmission electron microscopy (TEM) system. This AFM/STM-TEM system is used to investigate the mechanical, electrical, and electrochemical properties of boron nitride nanotubes (BNNTs) and Silicon nanorods (SiNRs). BNNTs are one of the subjects of this PhD research due to their comparable, and in some cases superior, properties compared to carbon nanotubes. Therefore, to further develop their applications, it is required to investigate these characteristics in atomic level. In this research, the mechanical properties of multi-walled BNNTs were first studied. Several tests were designed to study and characterize their real-time deformation behavior to the applied force. Observations revealed that BNNTs possess highly flexible structures under applied force. Detailed studies were then conducted to understand the bending mechanism of the BNNTs. Formations of reversible ripples were observed and described in terms of thermodynamic energy of the system. Fracture failure of BNNTs were initiated at the outermost walls and characterized to be brittle. Second, the electrical properties of individual BNNTs were studied. Results showed that the bandgap and electronic properties of BNNTs can be engineered by means of applied strain. It was found that the conductivity, electron concentration and carrier mobility of BNNTs can be tuned as a function of applied stress. Although, BNNTs are considered to be candidate for field emission applications, observations revealed that their properties degrade upon cycles of emissions. Results showed that due to the high emission current density, the temperature of the sample was increased and reached to the decomposition temperature at which the B-N bonds start to break. In addition to BNNTs, we have also performed in-situ study on the electrochemical properties of silicon nanorods (SiNRs). Specifically, lithiation and delithiation of SiNRs were studied by our STM-TEM system. Our observations showed the direct formation of Li22Si5 phases as a result of lithium intercalation. Radial expansion of the anode materials were observed and characterized in terms of size-scale. Later, the formation and growth of the lithium fibers on the surface of the anode materials were observed and studied. Results revealed the formation of lithium islands inside the ionic liquid electrolyte which then grew as Li dendrite toward the cathode material.

The Performance and Service Life Prediction of High Performance Concrete in Sulfate and Acidic Environments

Concrete substructures are often subjected to environmental deterioration, such as sulfate and acid attack, which leads to severe damage and causes structure degradation or even failure. In order to improve the durability of concrete, the High Performance Concrete (HPC) has become widely used by partially replacing cement with pozzolanic materials. However, HPC degradation mechanisms in sulfate and acidic environments are not completely understood. It is therefore important to evaluate the performance of the HPC in such conditions and predict concrete service life by establishing degradation models. This study began with a review of available environmental data in the State of Florida. A total of seven bridges have been inspected. Concrete cores were taken from these bridge piles and were subjected for microstructural analysis using Scanning Electron Microscope (SEM). Ettringite is found to be the products of sulfate attack in sulfate and acidic condition. In order to quantitatively analyze concrete deterioration level, an image processing program is designed using Matlab to obtain quantitative data. Crack percentage (Acrack/Asurface) is used to evaluate concrete deterioration. Thereafter, correlation analysis was performed to find the correlation between five related variables and concrete deterioration. Environmental sulfate concentration and bridge age were found to be positively correlated, while environmental pH level was found to be negatively correlated. Besides environmental conditions, concrete property factor was also included in the equation. It was derived from laboratory testing data. Experimental tests were carried out implementing accelerated expansion test under controlled environment. Specimens of eight different mix designs were prepared. The effect of pozzolanic replacement rate was taken into consideration in the empirical equation. And the empirical equation was validated with existing bridges. Results show that the proposed equations compared well with field test results with a maximum deviation of ± 20%. Two examples showing how to use the proposed equations are provided to guide the practical implementation. In conclusion, the proposed approach of relating microcracks to deterioration is a better method than existing diffusion and sorption models since sulfate attack cause cracking in concrete. Imaging technique provided in this study can also be used to quantitatively analyze concrete samples.

High-sensitivity differential scanning calorimetry for measurement of steroid entrapment in nebulised liposomes generated from proliposomes

A novel approach to the determination of steroid entrapment in the bilayers of aerosolised liposomes has been introduced using high-sensitivity differential scanning calorimetry (DSC). Proliposomes were dispersed in water within an air-jet nebuliser and the energy produced during atomisation was used to hydrate the proliposomes and generate liposome aerosols. Proliposomes that included the steroid beclometasone dipropionate (BDP) produced lower aerosol and lipid outputs than steroid-free proliposomes. Size analysis and transmission electron microscopy showed an evidence of liposome formation within the nebuliser, which was followed by deaggregation and size reduction of multilamellar liposomes on nebulisation to a two-stage impinger. For each formulation, no difference in thermal transitions was observed between delivered liposomes and those remaining in the nebuliser. However, steroid (5 mole%) lowered the onset temperature and the enthalpy of the pretransition, and produced a similar onset temperature and larger enthalpy of the main transition, with broadened pretransition and main transitions. This indicates that BDP was entrapped and exhibited an interaction with the liposome phospholipid membranes. Since the pretransition was depressed but not completely removed and no phase separation occurred, it is suggested that the bilayers of the multilamellar liposomes can entrap more than 5 mole% BDP. Overall, liposomes were generated from proliposomes and DSC investigations indicated that the steroid was entrapped in the bilayers of aerosolised multilamellar vesicles.

Insulator-to-metal transition in vanadium supersaturated silicon: variable-range hopping and Kondo effect signatures

We report the observation of the insulator-to-metal transition in crystalline silicon samples supersaturated with vanadium. Ion implantation followed by pulsed laser melting and rapid resolidification produce high quality single-crystalline silicon samples with vanadium concentrations that exceed equilibrium values in more than 5 orders of magnitude. Temperature-dependent analysis of the conductivity and Hall mobility values for temperatures from 10K to 300K indicate that a transition from an insulating to a metallic phase is obtained at a vanadium concentration between 1.1 × 10^(20) and 1.3 × 10^(21) cm^(−3) . Samples in the insulating phase present a variable-range hopping transport mechanism with a Coulomb gap at the Fermi energy level. Electron wave function localization length increases from 61 to 82 nm as the vanadium concentration increases in the films, supporting the theory of impurity band merging from delocalization of levels states. On the metallic phase, electronic transport present a dispersion mechanism related with the Kondo effect, suggesting the presence of local magnetic moments in the vanadium supersaturated silicon material.