Exploring thermal and mechanical properties of selected transition elements under extreme conditions: Experiments at high pressures and high temperatures

Transition metals (Ti, Zr, Hf, Mo, W, V, Nb, Ta, Pd, Pt, Cu, Ag, and Au) are essential building units of many materials and have important industrial applications. Therefore, it is important to understand their thermal and physical behavior when they are subjected to extreme conditions of pressure and temperature. This dissertation presents: • An improved experimental technique to use lasers for the measurement of thermal conductivity of materials under conditions of very high pressure (P, up to 50 GPa) and temperature (T up to 2500 K). • An experimental study of the phase relationship and physical properties of selected transition metals, which revealed new and unexpected physical effects of thermal conductivity in Zr, and Hf under high P-T. • New phase diagrams created for Hf, Ti and Zr from experimental data. • P-T dependence of the lattice parameters in α-hafnium. Contrary to prior reports, the α-ω phase transition in hafnium has a negative dT/dP slope. • New data on thermodynamic and physical properties of several transition metals and their respective high P-T phase diagrams. • First complete thermodynamic database for solid phases of 13 common transition metals was created. This database has: All the thermochemical data on these elements in their standard state (mostly available and compiled); All the equations of state (EoS) formulated from pressure-volume-temperature data (measured as a part of this study and from literature); Complete thermodynamic data for selected elements from standard to extreme conditions. The thermodynamic database provided by this study can be used with available thermodynamic software to calculate all thermophysical properties and phase diagrams at high P-T conditions. For readers who do not have access to this software, tabulated values of all thermodynamic and volume data for the 13 metals at high P-T are included in the APPENDIX. In the APPENDIX, a description of several other high-pressure studies of selected oxide systems is also included. Thermophysical properties (Cp, H, S, G) of the high P-T ω-phase of Ti, Zr and Hf were determined during the optimization of the EoS parameters and are presented in this study for the first time. These results should have important implications in understanding hexagonal-close-packed to simple-hexagonal phase transitions in transition metals and other materials.

Obesity and Serum High Sensitivity C-Reactive Protein Levels Among Elderly Turkish Immigrants in the Netherlands with Type 2 Diabetes

The study examined the associations of anthropometric measures of obesity with high sensitivity C-reactive protein (hs-CRP) levels in Turkish immigrants with type 2 diabetes (T2D) living in the Netherlands. A total of 110 participants, physician-diagnosed with T2D, aged 30 years and older were recruited from multiple sources from The Hague, Netherlands. Serum hs-CRP levels were measured with immunoturbidimetric assay. Glycated hemoglobin (A1C) was determined by high-pressure liquid chromatography. Measures of obesity: body weight, body mass index (BMI), waist circumference (WC), hip circumference (HC), waist-to-hip ratio (WHR), and waist-to-height ratio (WHtR) were determined. Statistical analysis included descriptive statistics, Pearson’s correlations and multiple linear regressions (MLR) stratified by gender. Hs-CRP was log transformed to achieve normality. Subjects with hs-CRP levels >10 mg/L (n = 17) were excluded from the analysis. Females had a higher BMI (p = 0.007), HC (p < 0.001), and WHtR (p = 0.011) as compared to males. Conversely, males had a higher weight (p = 0.007), and WHR (p < 0.001) than females. MLR showed that after controlling for covariates, log hs-CRP was positively associated with BMI (B = 0.039, SE = 0.019, β = 0.287, p < 0.05), WC (B = 0.025, SE = 0.011, β = 0.332, p < 0.05) and WHtR (B = 4.015, SE = 1.464, β = 0.376, p < 0.01) in females only. Gender-specific associations between obesity measures and hs-CRP level need to be further investigated in the Turkish immigrant population. Hs-CRP assessment may be added as a standard of care for T2D treatment within this population.

Study of Ammonia Borane and its Derivatives: Influence of Nanoconfinements and Pressures

Recently, ammonia borane has increasingly attracted researchers’ attention because of its merging applications, such as organic synthesis, boron nitride compounds synthesis, and hydrogen storage. This dissertation presents the results from several studies related to ammonia borane. The pressure-induced tetragonal to orthorhombic phase transition in ammonia borane was studied in a diamond anvil cell using in situ Raman spectroscopy. We found a positive Clapeyron-slope for this phase transformation in the experiment, which implies that the phase transition from tetragonal to orthorhombic is exothermic. The result of this study indicates that the rehydrogenation of the high pressure orthorhombic phase is expected to be easier than that of the ambient pressure tetragonal phase due to its lower enthalpy. The high pressure behavior of ammonia borane after thermal decomposition was studied by in situ Raman spectroscopy at high pressures up to 10 GPa. The sample of ammonia borane was first decomposed at ~140 degree Celcius and ~0.7 GPa and then compessed step wise in an isolated sample chamber of a diamond anvil cell for Raman spectroscopy measurement. We did not observe the characteristic shift of Raman mode under high pressure due to dihydrogen bonding, indicating that the dihydrogen bonding disappears in the decomposed ammonia borane. Although no chemical rehydrogenation was detected in this study, the decomposed ammonia borane could store extra hydrogen by physical absorption. The effect of nanoconfinement on ammonia borane at high pressures and different temperatures was studied. Ammonia borane was mixed with a type of mesoporous silica, SBA-15, and restricted within a small space of nanometer scale. The nano-scale ammonia borane was decomposed at ~125 degree Celcius in a diamond anvil cell and rehydrogenated after applying high pressures up to ~13 GPa at room temperature. The successful rehydrogenation of decomposed nano-scale ammonia borane gives guidance to further investigations on hydrogen storage. In addition, the high pressure behavior of lithium amidoborane, one derivative of ammonia borane, was studied at different temperatures. Lithium amidoborane (LAB) was decomposed and recompressed in a diamond anvil cell. After applying high pressures on the decomposed lithium amidoborane, its recovery peaks were discovered by Raman spectroscopy. This result suggests that the decomposition of LAB is reversible at high pressures.

Surface temperature reconstruction using alkenones from sediment core B0406 retreived in the Peru upwelling area

We reconstructed a high-resolution, alkenone-based sea surface temperature (SST) record spanning the last ca. 150 years, from a sediment core retrieved within the main upwelling zone off Peru. A conspicuous SST decline is evidenced since the 1950s despite interdecadal SST variability. Instrumental SST data and reanalysis of ECMWF ERA 40 winds suggest that the recent coastal cooling corresponds mainly to an intensification of alongshore winds and associated increase of upwelling in spring. Consistently, both proxy and instrumental data evidence increased productivity in phase with the SST cooling. Our data expand on previous reports on recent SST cooling in other Eastern Boundary upwelling systems and support scenarios that relate coastal upwelling intensification to global warming. Yet, further investigations are needed to assess the role of different mechanisms and forcings (enhanced local winds vs. spin-up of the South Pacific High Pressure cell).

Sedimentology of the Okhotsk Sea

On the basis of two sedimentary records from the central Sea of Okhotsk, we reconstruct the closely coupled glacial/interglacial changes in terrigenous flux, marine productivity, and sea ice coverage over the past 1.1 Myr. The correspondance of our sedimentary records to the China loess grain size record (China loess particle timescale, CHILOPARTS) suggests that environmental changes in both the Sea of Okhotsk area and in SE Asia were closely related via the Siberian atmospheric high-pressure cell. During full glacial times our records point to a strong Siberian High causing northerly wind directions, the extension of the sea ice cover, and a reduced Amur River discharge. Deglacial maxima of terrigenous flux were succeeded by or synchronous to high-productivity events. Marine productivity was strengthened during glacial terminations because of an effective nutrient utilization at times of enhanced water column stratification and high nutrient supply from fluvial runoff and sea ice thawing. During interglacials, SE monsoonal winds prevailed, analogous to today's summer situation of a pronounced Mongolian Heat Low and a strong Hawaiian High. Strong freshwater discharge induced by high precipitation rates in the Amur drainage area and a seasonally reduced and mobile sea ice cover favored marine productivity (although being considerably lower than during the terminations) and a lowered flux of ice-rafted detritus.

Avaliação das condições de precipitação do azul da Prússia sobre pó de grafite visando o desenvolvimento de eletrodos de pasta de carbono para a quantificação de nitrito

An amperometric FIA method for nitrite quantification based on nitrite electroreduction and employing a carbon paste electrode (CPE) chemically modified with iron hexacyanoferrate (HCF) as an amperometric detector was developed. The influence of experimental conditions on the preparation of the electrode materials was evaluated and the materials obtained in each study were used for the development of modified electrodes. The electrochemical sensors were prepared by a fast, simple, and inexpensive procedure, and the long-term performance of the electrodes were quite satisfactory as the stability was maintained over one year. HCF was an effective redox mediator for nitrite electroreduction in acidic media, allowing nitrite detection at +0.2 V vs. Ag/AgClsat, which is a potential free of possible interfering species that are normally present in food and water samples. The electrochemical cell used in the FIA system was similar to a batch injection analysis cell, enabling recirculation of the carrier solution. This is an attractive feature because it allows the use of a high flow rate (6 mL min-1) leading to high sensitivity and analysis speed, while keeping reagent consumption low. The proposed method had a detection limit of 9 μmol L-1 and was successfully employed for nitrite quantification in spiked water and sausage samples. The obtained results were in good agreement with those provided by the spectrophotometric official method. At a 95 % confidence level it was not observed statistical differences neither in nitrite content nor in the precision provided by both methods. The experimental conditions for the synthesis of HCF were optimized and the best electrode material was prepared by mixing FeCl3, K4[Fe(CN)6] and carbon powder subjected to an acid and thermal treatment (400 ºC), followed by ultrasonic agitation at 4 °C. This material was used to construct an electrode with improved analytical performance to reduce nitrite, which presented greater stability compared to HCF film electrodeposited on the EPC, showing that the preparation procedure of the electrode material is an effective strategy for the development of HCF modified electrodes.

Chemical characterization and evaluation of biological activity of Cynara cardunculus extractable compounds

The Mediterranean species Cynara cardunculus L. is recognized in the traditional medicine, for their hepatoprotective and choleretic effects. Biomass of C. cardunculus L. var. altilis (DC), or cultivated cardoon, may be explored not only for the production of energy and pulp fibers, but also for the extraction of bioactive compounds. The chemical characterization of extractable components, namely terpenic and phenolic compounds, may valorize the cultivated cardoon plantation, due to their antioxidant, antitumoral and antimicrobial activities. In this study, the chemical composition of lipophilic and phenolic fractions of C. cardunculus L. var. altilis (DC), cultivated in the south of Portugal (Baixo Alentejo region) was characterized in detail, intending the integral valorization of its biomass. The biological activity of cultivated cardoon extracts was evaluated in terms of antioxidant, human tumor cell antiproliferative and antibacterial effects. Gas chromatography-mass spectrometry (GC-MS) was used for the chemical analysis of lipophilic compounds. Sixty-five lipophilic compounds were identified, from which 1 sesquiterpene lactone and 4 pentacyclic triterpenes were described, for the first time, as cultivated cardoon components, such as: deacylcynaropicrin, acetates of β- and α-amyrin, lupenyl acetate and ψ-taraxasteryl acetate. Sesquiterpene lactones were the major family of lipophilic components of leaves (≈94.5 g/kg), mostly represented by cynaropicrin (≈87.4 g/kg). Pentacyclic triterpenes were also detected, in considerably high contents, in the remaining parts of cultivated cardoon, especially in the florets (≈27.5 g/kg). Taraxasteryl acetate was the main pentacyclic triterpene (≈8.9 g/kg in florets). High pressure liquid chromatography-mass spectrometry (HPLC-MS) was utilized for the chemical analysis of phenolic compounds. Among the identified 28 phenolic compounds, eriodictyol hexoside was reported for the first time as C. cardunculus L. component, and 6 as cultivated cardoon components, namely 1,4-di-O-caffeoylquinic acid, naringenin 7-O-glucoside, naringenin rutinoside, naringenin, luteolin acetylhexoside and apigenin acetylhexoside. The highest content of the identified phenolic compounds was observed in the florets (≈12.6 g/kg). Stalks outer part contained the highest hydroxycinnamic acids abundance (≈10.3 g/kg), and florets presented the highest flavonoids content (≈10.3 g/kg). The antioxidant activity of phenolic fraction was examined through 2,2-diphenyl-1-picrylhydrazyl (DPPH) free radical scavenging assay. Stalks outer part, and receptacles and bracts extracts demonstrated the highest antioxidant effect on DPPH (IC50 of 34.35 μg/mL and 35.25 μg/mL, respectively). (cont.) abstract (cont.) The DPPH scavenging effect was linearly correlated with the total contents of hydroxycinnamic acids (r = -0.990). The in vitro antiproliferative activity of cultivated cardoon lipophilic and phenolic extracts was evaluated on a human tumor cells line of triple-negative breast cancer (MDA-MB-231), one of the most refractory human cancers to conventional therapeutics. After 48 h of exposition, leaves lipophilic extract showed higher inhibitory effect (IC50 = 10.39 μg/mL) than florets lipophilic extract (IC50 = 315.22 μg/mL), upon MDA-MB-231 cellular viability. Pure compound of cynaropicrin, representative of the main compound identified in leaves lipophilic extract, also prevented the cell proliferation of MDA-MB-231 (IC50 = 17.86 μM). MDA-MB-231 cells were much more resistant to the 48 h- treatment with phenolic extracts of stalks outer part (IC50 = 3341.20 μg/mL) and florets (IC50 > 4500 μg/mL), and also with the pure compound of 1,5-di-O-caffeoylquinic acid (IC50 = 1741.69 μM). MDA-MB-231 cells were exposed, for 48 h, to the respective IC50 concentrations of leaves lipophilic extract and pure compound of cynaropicrin, in order to understand their ability in modelling cellular responses, and consequently important potentially signaling pathways for the cellular viability decrease. Leaves lipophilic extract increased the caspase-3 enzymatic activity, contrarily to pure compound of cynaropicrin. Additionally, leaves lipophilic extract and pure compound of cynaropicrin caused G2 cell cycle arrest, possibly by upregulating the p21Waf1/Cip1 and the accumulation of phospho-Tyr15-CDK1 and cyclin B1. The inhibitory effects of leaves lipophilic extract and cynaropicrin pure compound, against the MDA-MB-231 cell proliferation, may also be related to the downregulation of phospho-Ser473-Akt. The antibacterial activity of cultivated cardoon lipophilic and phenolic extracts was assessed, for the first time, on two multidrug-resistant bacteria, such as the Gram-negative Pseudomonas aeruginosa PAO1 and the Gram-positive methicillin-resistant Staphylococcus aureus (MRSA), two of the main bacteria responsible for health care-associated infections. Accordingly, the minimum inhibitory concentrations (MIC) were determined. Lipophilic and phenolic extracts of florets did not have antibacterial activity on P. aeruginosa PAO1 and MRSA (MIC > 2048 μg/mL). Leaves lipophilic extract did not prevent the P. aeruginosa PAO1 growth, but pure compound of cynaropicrin was slightly active (MIC = 2048 μg/mL). Leaves lipophilic extract and pure compound of cynaropicrin blocked MRSA growth (MIC of 1024 and 256 μg/mL, respectively). The scientific knowledge revealed in this thesis, either by the chemical viewpoint, or by the biological viewpoint, contributes for the valorization of C. cardunculus L. var. altilis (DC) biomass. Cultivated cardoon has potential to be exploited as source of bioactive compounds, in conciliation with other valorization pathways, and Portuguese traditional cheeses manufacturing.

Tris(2-ethylhexyl) trimellitate (TOTM) as a potential industrial reference fluid for viscosity at high temperatures and high pressures: New viscosity, density and surface tension measurements

Tris(2-ethylhexyl) trimellitate (TOTM) was recently suggested as a reference fluid for industrial use associated with high viscosity at elevated temperature and pressure. Viscosity and density data have already been published on one sample covering the temperature range (303-373) K and at pressures up to about 65 MPa. The viscosity covered a range from about (9 to 460) mPa s. In the present article we study several other characteristics of TOTM that must be available if it were to be adopted as a standard. First, we present values for the viscosity and density obtained with a different sample of TOTM to examine the important feature of consistency among different samples. Vibrating-wire viscosity measurements were performed at pressures from (5 to 100) MPa, along 6 isotherms between (303 and 373) K. Density measurements were carried out from (293 to 373) K up to 68 MPa, along 4 isotherms, using an Anton Paar DMA HP vibrating U-tube densimeter. Secondly, we report a study of the effect of water contamination on the viscosity of TOTM, performed using an Ubbelhode viscometer under atmospheric pressure. Finally, in order to support the use of TOTM as a reference liquid for the calibration of capillary viscometers, values of its surface tension, obtained by the pendant drop method, are provided. (C) 2016 Elsevier B.V. All rights reserved.

Exploring complex chemical systems: insights from mass spectrometry, electrochemistry and continuous cell culture

The work presented herein covers a broad range of research topics and so, in the interest of clarity, has been presented in a portfolio format. Accordingly, each chapter consists of its own introductory material prior to presentation of the key results garnered, this is then proceeded by a short discussion on their significance. In the first chapter, a methodology to facilitate the resolution and qualitative assessment of very large inorganic polyoxometalates was designed and implemented employing ion-mobility mass spectrometry. Furthermore, the potential of this technique for ‘mapping’ the conformational space occupied by this class of materials was demonstrated. These claims are then substantiated by the development of a tuneable, polyoxometalate-based calibration protocol that provided the necessary platform for quantitative assessments of similarly large, but unknown, polyoxometalate species. In addition, whilst addressing a major limitation of travelling wave ion mobility, this result also highlighted the potential of this technique for solution-phase cluster discovery. The second chapter reports on the application of a biophotovoltaic electrochemical cell for characterising the electrogenic activity inherent to a number of mutant Synechocystis strains. The intention was to determine the key components in the photosynthetic electron transport chain responsible for extracellular electron transfer. This would help to address the significant lack of mechanistic understanding in this field. Finally, in the third chapter, the design and fabrication of a low-cost, highly modular, continuous cell culture system is presented. To demonstrate the advantages and suitability of this platform for experimental evolution investigations, an exploration into the photophysiological response to gradual iron limitation, in both the ancestral wild type and a randomly generated mutant library population, was undertaken. Furthermore, coupling random mutagenesis to continuous culture in this way is shown to constitute a novel source of genetic variation that is open to further investigation.

Computational modelling of non-equilibrium condensing steam flows in low-pressure steam turbines

The steam turbines play a significant role in global power generation. Especially, research on low pressure (LP) steam turbine stages is of special importance for steam turbine man- ufactures, vendors, power plant owners and the scientific community due to their lower efficiency than the high pressure steam turbine stages. Because of condensation, the last stages of LP turbine experience irreversible thermodynamic losses, aerodynamic losses and erosion in turbine blades. Additionally, an LP steam turbine requires maintenance due to moisture generation, and therefore, it is also affecting on the turbine reliability. Therefore, the design of energy efficient LP steam turbines requires a comprehensive analysis of condensation phenomena and corresponding losses occurring in the steam tur- bine either by experiments or with numerical simulations. The aim of the present work is to apply computational fluid dynamics (CFD) to enhance the existing knowledge and understanding of condensing steam flows and loss mechanisms that occur due to the irre- versible heat and mass transfer during the condensation process in an LP steam turbine. Throughout this work, two commercial CFD codes were used to model non-equilibrium condensing steam flows. The Eulerian-Eulerian approach was utilised in which the mix- ture of vapour and liquid phases was solved by Reynolds-averaged Navier-Stokes equa- tions. The nucleation process was modelled with the classical nucleation theory, and two different droplet growth models were used to predict the droplet growth rate. The flow turbulence was solved by employing the standard k-ε and the shear stress transport k-ω turbulence models. Further, both models were modified and implemented in the CFD codes. The thermodynamic properties of vapour and liquid phases were evaluated with real gas models. In this thesis, various topics, namely the influence of real gas properties, turbulence mod- elling, unsteadiness and the blade trailing edge shape on wet-steam flows, are studied with different convergent-divergent nozzles, turbine stator cascade and 3D turbine stator-rotor stage. The simulated results of this study were evaluated and discussed together with the available experimental data in the literature. The grid independence study revealed that an adequate grid size is required to capture correct trends of condensation phenomena in LP turbine flows. The study shows that accurate real gas properties are important for the precise modelling of non-equilibrium condensing steam flows. The turbulence modelling revealed that the flow expansion and subsequently the rate of formation of liquid droplet nuclei and its growth process were affected by the turbulence modelling. The losses were rather sensitive to turbulence modelling as well. Based on the presented results, it could be observed that the correct computational prediction of wet-steam flows in the LP turbine requires the turbulence to be modelled accurately. The trailing edge shape of the LP turbine blades influenced the liquid droplet formulation, distribution and sizes, and loss generation. The study shows that the semicircular trailing edge shape predicted the smallest droplet sizes. The square trailing edge shape estimated greater losses. The analysis of steady and unsteady calculations of wet-steam flow exhibited that in unsteady simulations, the interaction of wakes in the rotor blade row affected the flow field. The flow unsteadiness influenced the nucleation and droplet growth processes due to the fluctuation in the Wilson point.

Evaluation of Adoptive T Cell Therapy and Oncolytic Virotherapy for Treatment of Brain Tumors

Adoptive immunotherapy and oncolytic virotherapy are two promising strategies for treating primary and metastatic malignant brain tumors. We demonstrate the ability of adoptively transferred tumor-specific T cells to rapidly mediate the clearance of established brain tumors in several mouse models. Similar to the clinical situation, tumor recurrences are frequent and result from immune editing of tumors. T cells can eliminate antigen-expressing tumor cells but are not effective against antigen loss variant (ALV) cancer cells that multiply and repopulate a tumor. We show that the level of tumor antigen present affects the success of adoptive T cell therapy. When high levels of antigen are present, tumor stromal cells such as microglia and macrophages present tumor peptide on their surface. As a result, T cells directly eliminate cancer cells and cross-presenting stromal cells and indirectly eliminate ALV cells. We were able to show the first direct evidence of tumor antigen cross-presentation by CD11b+ stromal cells in the brain using soluble, high-affinity T cell receptor monomers. Strategies that target brain tumor stroma or increase antigen shedding from tumor cells leading to increased crosspresentation by stromal cells may improve the clinical success of T cell adoptive therapies. We evaluated one potential strategy to complement adoptive T cell therapy by characterizing the oncolytic effects of myxoma virus (MYXV) in a syngeneic mouse brain tumor model of metastatic melanoma. MYXV is a rabbit poxvirus with strict species tropism for European rabbits. MYXV can also infect mouse and human cancer cell lines due to signaling defects in innate antiviral mechanisms and hyperphosphorylation of Akt. MYXV kills B16.SIY melanoma cells in vitro, and intratumoral injection of virus leads to robust, selective and transient infection of the tumor. We observed that virus treatment recruits innate immune cells iii to the tumor, induces TNFα and IFNβ production in the brain, and results in limited oncolytic effects in vivo. To overcome this, we evaluated the safety and efficacy of co-administering 2C T cells, MYXV, and neutralizing antibodies against IFNβ. Mice that received the triple combination therapy survived significantly longer with no apparent side effects, but eventually relapsed. Based on these findings, methods to enhance viral replication in the tumor and limit immune clearance of the virus will be pursued. We conclude that myxoma virus should be further explored as a vector for transient delivery of therapeutic genes to a tumor to enhance T cell responses.

Desenvolvimento de uma célula a combustível de glicerol direto em meio alcalino

Dissertação (mestrado)—Universidade de Brasília, Instituto de Química, Programa de Pós-Graduação em Química, 2015.

Desenvolvimento de uma célula a combustível de glicerol direto em meio alcalino

Dissertação (mestrado)—Universidade de Brasília, Instituto de Química, Programa de Pós-Graduação em Química, 2015.

Effect of pre-treatments and post-treatments on drying products

Freeze drying technology can give good quality attributes of vegetables and fruits in terms of color, nutrition, volume, rehydration kinetics, stability during storage, among others, when compared with solely air dried ones. However, published scientific works showed that treatments applied before and after air dehydration are effective in food attributes, improving its quality. Therefore, the hypothesis of the present thesis was focus in a vast research of scientific work that showed the possibility to apply a pre-treatment and a post-treatment to food products combined with conventional air drying aiming being close, or even better, to the quality that a freeze dried product can give. Such attributes are the enzymatic inactivation, stability during storage, drying and rehydration kinetics, color, nutrition, volume and texture/structure. With regard to pre-treatments, the ones studied along the present work were: water blanching, steam blanching, ultrasound, freezing, high pressure and osmotic dehydration. High electric pulsed field was also studied but the food attributes were not explained on detailed. Basically, water and steam blanching showed to be adequate to inactivate enzymes in order to prevent enzymatic browning and preserve the product quality during long storage periods. With regard to ultrasound pre-treatment the published results pointed that ultrasound is an effective pre-treatment to reduce further drying times, improve rehydration kinetics and color retention. On the other hand, studies showed that ultrasound allow sugars losses and, in some cases, can lead to cell disruption. For freezing pre-treatment an overall conclusion was difficult to draw for some food attributes, since, each fruit or vegetable is unique and freezing comprises a lot of variables. However, for the studied cases, freezing showed to be a pre-treatment able to enhance rehydration kinetics and color attributes. High pressure pre-treatment showed to inactivate enzymes improving storage stability of food and showed to have a positive performance in terms of rehydration. For other attributes, when high pressure technology was applied, the literature showed divergent results according with the crops used. Finally, osmotic dehydration has been widely used in food processing to incorporate a desired salt or sugar present in aqueous solution into the cellular structure of food matrix (improvement of nutrition attribute). Moreover, osmotic dehydration lead to shorter drying times and the impregnation of solutes during osmose allow cellular strengthens of food. In case of post-treatments, puffing and a new technology denominated as instant controlled pressure drop (DIC) were reported in the literature as treatments able to improve diverse Abstract Effect of Pre-treatments and Post-treatments on Drying Products x food attributes. Basically, both technologies are similar where the product is submitted to a high pressure step and the process can make use of different heating mediums such as CO2, steam, air and N2. However, there exist a significant difference related with the final stage of both which can comprise the quality of the final product. On the other hand, puffing and DIC are used to expand cellular tissues improving the volume of food samples, helping in rehydration kinetics as posterior procedure, among others. The effectiveness of such pre and/or post-treatments is dependent on the state of the vegetables and fruits used which are also dependent of its cellular structure, variety, origin, state (fresh, ripe, raw), harvesting conditions, etc. In conclusion, as it was seen in the open literature, the application of pre-treatments and post-treatments coupled with a conventional air dehydration aim to give dehydrated food products with similar quality of freeze dried ones. Along the present Master thesis the experimental data was removed due to confidential reasons of the company Unilever R&D Vlaardingen

Study of ammonia borane and its derivatives: Influence of nanoconfinements and pressures

Recently, ammonia borane has increasingly attracted researchers’ attention because of its merging applications, such as organic synthesis, boron nitride compounds synthesis, and hydrogen storage. This dissertation presents the results from several studies related to ammonia borane. ^ The pressure-induced tetragonal to orthorhombic phase transition in ammonia borane was studied in a diamond anvil cell using in situ Raman spectroscopy. We found a positive Clapeyron-slope for this phase transformation in the experiment, which implies that the phase transition from tetragonal to orthorhombic is exothermic. The result of this study indicates that the rehydrogenation of the high pressure orthorhombic phase is expected to be easier than that of the ambient pressure tetragonal phase due to its lower enthalpy. ^ The high pressure behavior of ammonia borane after thermal decomposition was studied by in situ Raman spectroscopy at high pressures up to 10 GPa. The sample of ammonia borane was first decomposed at ∼140 degree Celcius and ∼0.7 GPa and then compessed step wise in an isolated sample chamber of a diamond anvil cell for Raman spectroscopy measurement. We did not observe the characteristic shift of Raman mode under high pressure due to dihydrogen bonding, indicating that the dihydrogen bonding disappears in the decomposed ammonia borane. Although no chemical rehydrogenation was detected in this study, the decomposed ammonia borane could store extra hydrogen by physical absorption. ^ The effect of nanoconfinement on ammonia borane at high pressures and different temperatures was studied. Ammonia borane was mixed with a type of mesoporous silica, SBA-15, and restricted within a small space of nanometer scale. The nano-scale ammonia borane was decomposed at ∼125 degree Celcius in a diamond anvil cell and rehydrogenated after applying high pressures up to ∼13 GPa at room temperature. The successful rehydrogenation of decomposed nano-scale ammonia borane gives guidance to further investigations on hydrogen storage. ^ In addition, the high pressure behavior of lithium amidoborane, one derivative of ammonia borane, was studied at different temperatures. Lithium amidoborane (LAB) was decomposed and recompressed in a diamond anvil cell. After applying high pressures on the decomposed lithium amidoborane, its recovery peaks were discovered by Raman spectroscopy. This result suggests that the decomposition of LAB is reversible at high pressures.^