Study of the effect of minor compounds on the oxidative stability and physical properties of bulk oil, oil-in-water emulsion, and food emulsions

Minor components are of particular interest due to their antioxidant and biological properties. Various classes of lipophilic minor components (plant sterols (PS) and α-tocopherol) were selected as they are widely used in the food industry. A Fast GC-MS method for PS analysis in functional dairy products was set up. The analytical performance and significant reduction of the analysis time and consumables, demonstrated that Fast GC-MS could be suitable for the PS analysis in functional dairy products. Due to their chemical structure, PS can undergo oxidation, which could be greatly impacted by matrix nature/composition and thermal treatments. The oxidative stability of PS during microwave heating was evaluated. Two different model systems (PS alone and in combination) were heated up to 30 min at 1000 W. PS degraded faster when they were alone than in presence of TAG. The extent of PS degradation depends on both heating time and the surrounding medium, which can impact the quality and safety of the food product destined to microwave heating/cooking. Many minor lipid components are included in emulsion systems and can affect the rate of lipid oxidation. The oxidative stability of oil-in-water (O/W) emulsions containing PS esters, ω-3 FA and phenolic compounds, were evaluated after a 14-day storage at room temperature. Due to their surface active character, PS could be particularly prone to oxidation when they are incorporated in emulsions, as they are more exposed to water-soluble prooxidants. Finally, some minor lipophilic components may increase oxidative stability of food systems due to their antioxidant activity. á-tocopherol partitioning and antioxidant activity was determined in the presence of excess SDS in stripped soybean O/W emulsions. Results showed that surfactant micelles could play a key role as an antioxidant carrier, by potentially increasing the accessibility of hydrophobic antioxidant to the interface.

Morphological and optical properties of SiON thin films for photovoltaic applications

In the last years technologies related to photovoltaic energy have rapidly developed and the interest on renewable energy power source substantially increased. In particular, cost reduction and appropriate feed-in tariff contributed to the increase of photovoltaic installation, especially in Germany and Italy. However, for several technologies, the observed experimental efficiency of solar cells is still far from the theoretical maximum efficiency, and thus there is still room for improvement. In this framework the research and development of new materials and new solar devices is mandatory. In this thesis the morphological and optical properties of thin films of nanocrystalline silicon oxynitride (nc-SiON) have been investigated. This material has been studied in view of its application in Si based heterojunction solar cells (HIT). Actually, a-Si:H is used now in these cells as emitter layer. Amorphous SiO_x N_y has already shown excellent properties, such as: electrical conductivity, optical energy gap and transmittance higher than the ones of a-Si:H. Nc-SiO_x N_y has never been investigated up to now, but its properties can surpass the ones of amorphous SiON. The films of nc-SiON have been deposited at the University of Konstanz (Germany). The properties of these films have been studied using of atomic force microscopy and optical spectroscopy methods. This material is highly complex as it is made by different coexisting phases. The main purpose of this thesis is the development of methods for the analyses of morphological and optical properties of nc-SiON and the study of the reliability of those methods to the measurement of the characteristics of these silicon films. The collected data will be used to understand the evolution of the properties of nc-SiON, as a function of the deposition parameters. The results here obtained show that nc-SiON films have better properties with respect to both a-Si:H and a-SiON, i. e. higher optical band-gap and transmittance. In addition, the analysis of the variation of the observed properties as a function of the deposition parameters allows for the optimization of deposition conditions for obtaining optimal efficiency of a HIT cell with SiON layer.

Effects Of The Flash Welding Process On Mechanical And Microstructural Properties Of Structural Steel Joints Assessed Using Dest

ASTM A529 carbon¿manganese steel angle specimens were joined by flash butt welding and the effects of varying process parameter settings on the resulting welds were investigated. The weld metal and heat affected zones were examined and tested using tensile testing, ultrasonic scanning, Rockwell hardness testing, optical microscopy, and scanning electron microscopy with energy dispersive spectroscopy in order to quantify the effect of process variables on weld quality. Statistical analysis of experimental tensile and ultrasonic scanning data highlighted the sensitivity of weld strength and the presence of weld zone inclusions and interfacial defects to the process factors of upset current, flashing time duration, and upset dimension. Subsequent microstructural analysis revealed various phases within the weld and heat affected zone, including acicular ferrite, Widmanstätten or side-plate ferrite, and grain boundary ferrite. Inspection of the fracture surfaces of multiple tensile specimens, with scanning electron microscopy, displayed evidence of brittle cleavage fracture within the weld zone for certain factor combinations. Test results also indicated that hardness was increased in the weld zone for all specimens, which can be attributed to the extensive deformation of the upset operation. The significance of weld process factor levels on microstructure, fracture characteristics, and weld zone strength was analyzed. The relationships between significant flash welding process variables and weld quality metrics as applied to ASTM A529-Grade 50 steel angle were formalized in empirical process models.

The histological features and physical properties of eroded dental hard tissues.

Erosive demineralisation causes characteristic histological features. In enamel, mineral is dissolved from the surface, resulting in a roughened structure similar to an etching pattern. If the acid impact continues, the initial surface mineral loss turns into bulk tissue loss and with time a visible defect can develop. The microhardness of the remaining surface is reduced, increasing the susceptibility to physical wear. The histology of eroded dentine is much more complex because the mineral component of the tissue is dissolved by acids whereas the organic part is remaining. At least in experimental erosion, a distinct zone of demineralised organic material develops, the thickness of which depends on the acid impact. This structure is of importance for many aspects, e.g. the progression rate or the interaction with active agents and physical impacts, and needs to be considered when quantifying mineral loss. The histology of experimental erosion is increasingly well understood, but there is lack of knowledge about the histology of in vivo lesions. For enamel erosion, it is reasonable to assume that the principal features may be similar, but the fate of the demineralised dentine matrix in the oral cavity is unclear. As dentine lesions normally appear hard clinically, it can be assumed that it is degraded by the variety of enzymes present in the oral cavity. Erosive tooth wear may lead to the formation of reactionary or reparative dentine.

Synthesis and Thermodynamic and Biophysical Properties of Tricyclo-DNA

The DNA analogue tricyclo-DNA, built from conformationally rigid nucleoside analogues that were linked via tertiary phosphodiester functions, can efficiently be synthesized from the corresponding phosphoramidites by conventional solid-phase cyanoethyl phosphoramidite chemistry. 5'-End phosphorylated tricyclo-DNA sequences are chemically stable in aqueous, pH-neutral media at temperatures from 0 to 90 C. Tricyclo-DNA sequences resist enzymatic hydrolysis by the 3'-exonuclease snake venom phosphodiesterase. Homobasic adenine- and thymine-containing tricyclo-DNA octa- and nonamers are extraordinarily stable A-T base-pairing systems, not only in their own series but also with complementary DNA and RNA. Base mismatch formation is strongly destabilized. As in bicyclo-DNA, the tricyclo-DNA purine sequences preferentially accept a complementary strand on the Hoogsteen face of the base. A thermodynamic analysis reveals entropic benefits in the case of hetero-backbone duplex formation (tricyclo-DNA/DNA duplexes) and both an enthalpic and entropic benefit for duplex formation in the pure tricyclo-DNA series compared to natural DNA. Stability of tricyclo-DNA duplex formation depends more strongly on monovalent salt concentration compared to natural DNA. Homopyrimidine DNA sequences containing tricyclothymidine residues form triplexes with complementary double-stranded DNA. Triple-helix stability depends on the sequence composition and can be higher when compared to that of natural DNA. The use of one tricyclothymidine residue in the center of the self-complementary dodecamer duplex (d(CGCGAAT t CGCG), t = tricyclothymidine) strongly stabilizes its monomolecular hairpin loop structure relative to that of the corresponding pure DNA dodecamer ( T m = +20 C), indicating (tetra)loop-stabilizing properties of this rigid nucleoside analogue.

Nucleic-Acid Analogs with Restricted Conformational Flexibility in the Sugar-Phosphate Backbone (‘Bicyclo-DNA’). Part 5. Synthesis, Characterization, and Pairing Properties of Oligo-αlpha-D-(bicyclodeoxynucleotides) of the Bases Adenine and Thymine (αlpha-Bicyclo-DNA)

10.1002/hlca.19950780816.abs A conformational analysis of the (3′S,5′R)-2′-deoxy-3′,5′-ethano-α-D-ribonucleosides (a-D-bicyclodeoxynucleosides) based on the X-ray analysis of N4-benzoyl-α-D-(bicyclodeoxycytidine) 6 and on 1H-NMR analysis of the α-D-bicyclodeoxynucleoside derivatives 1-7 reveals a rigid sugar structure with the furanose units in the l′-exo/2′-endo conformation and the secondary OH groups on the carbocyclic ring in the pseudoequatorial orientation. Oligonucleotides consisting of α-D-bicyclothymidine and α-D-bicyclodeoxyadenosine were successfully synthesized from the corresponding nucleosides by phosphoramidite methodology on a DNA synthesizer. An evaluation of their pairing properties with complementary natural RNA and DNA by means of UV/melting curves and CD spectroscopy show the following characteristics: i) α-bcd(A10) and α-bcd(T10) (α = short form of α-D)efficiently form complexes with complementary natural DNA and RNA. The stability of these hybrids is comparable or slightly lower as those with natural β-d(A10) or β-d(T10)( β = short form ofβ-D). ii) The strand orientation in α-bicyclo-DNA/β-DNA duplexes is parallel as was deduced from UV/melting curves of decamers with nonsymmetric base sequences. iii) CD Spectroscopy shows significant structural differences between α-bicyclo-DNA/β-DNA duplexes compared to α-DNA/β-DNA duplexes. Furthermore, α-bicyclo-DNA is ca. 100-fold more resistant to the enzyme snake-venom phosphodiesterase with respect to β-DNA and about equally resistant as α-DNA.

Structural elucidation and antisense properties of a sugar-modified DNA analogue

Antisense oligonucleotides deserve great attention as potential drug candidates for the treatment of genetic disorders. For example, muscle dystrophy can be treated successfully in mice by antisense-induced exon skipping in the pre-mRNA coding for the structural protein dystrophin in muscle cells. For this purpose a sugar- and backbone-modified DNA analogue was designed, in which a tricyclic ring system substitutes the deoxyribose. These chemical modifications stabilize the dimers formed with the targeted RNA relative to native nucleic acid duplexes and increase the biostability of the antisense oligonucleotide. While evading enzymatic degradation constitutes an essential property of antisense oligonucleotides for therapeutic application, it renders the oligonucleotide inaccessible to biochemical sequencing techniques and requires the development of alternative methods based on mass spectrometry. The set of sequences studied includes tcDNA oligonucleotides ranging from 10 to 15 nucleotides in length as well as their hybrid duplexes with DNA and RNA complements. All samples were analyzed on a LTQ Orbitrap XL instrument equipped with a nano-electrospray source. For tandem mass spectrometric experiments collision-induced dissociation was performed, using helium as collision gas. Mass spectrometric sequencing of tcDNA oligomers manifests the applicability of the technique to substrates beyond the scope of enzyme-based methods. Sequencing requires the formation of characteristic backbone fragments, which take the form of a-B- and w-ions in the product ion spectra of tcDNA. These types of product ions are typically associated with unmodified DNA, which suggests a DNA-like fragmentation mechanism in tcDNA. The loss of nucleobases constitutes the second prevalent dissociation pathway observed in tcDNA. Comparison of partially and fully modified oligonucleotides indicates a pronounced impact of the sugar-moiety on the base loss. As this event initiates cleavage of the backbone, the presented results provide new mechanistic insights into the fragmentation of DNA in the gas-phase. The influence of the sugar-moiety on the dissociation extends to tcDNA:DNA and tcDNA:RNA hybrid duplexes, where base loss was found to be much more prominent from sugar-modified oligonucleotides than from their natural complements. Further prominent dissociation channels are strand separation and backbone cleavage of the single strands, as well as the ejection of backbone fragments from the intact duplex. The latter pathway depends noticeably on the base sequence. Moreover, it gives evidence of the high stability of the hybrid dimers, and thus directly reflects the affinity of tcDNA for its target in the cell. As the cellular target of tcDNA is a pre-mRNA, the structure was designed to discriminate RNA from DNA complements, which could be demonstrated by mass spectrometric experiments.

Anelastic strain recovery and elastic properties of ODP Leg 123 oceanic basalt samples

A knowledge of rock stress is fundamental for improving our understanding of oceanic crustal mechanisms and lithospheric dynamic processes. However, direct measurements of stress in the deep oceans, and in particular stress magnitudes, have proved to be technically difficult. Anelastic strain recovery measurements were conducted on 15 basalt core samples from Sites 765 and 766 during Leg 123. Three sets of experiments were performed: anelastic strain recovery monitoring, dynamic elastic property measurements, and thermal azimuthal anisotropy observations. In addition, a range of other tests and observations were recorded to characterize each of the samples. One common feature of the experimental results and observations is that apparently no consistent orientation trend exists, either between the different measurements on each core sample or between the same sets of measurements on the various core samples. However, some evidence of correspondence between velocity anisotropy and anelastic strain recovery exists, but this is not consistent for all the core samples investigated. Thermal azimuthal anisotropy observations, although showing no conclusive correlations with the other results, were of significant interest in that they clearly exhibited anisotropic behavior. The apparent reproducibility of this behavior may point toward the possibility of rocks that retain a "memory" of their stress history, which could be exploited to derive stress orientations from archived core. Anelastic strain recovery is a relatively new technique. Because use of the method has extended to a wider range of rock types, the literature has begun to include examples of rocks that contracted with time. Strong circumstantial evidence exists to suggest that core-sample contractions result from the slow diffusion of pore fluids from a preexisting microcrack structure that permits the rock to deflate at a greater rate than the expansion caused by anelastic strain recovery. Both expansions and contractions of the Leg 123 cores were observed. The basalt cores have clearly been intersected by an abundance of preexisting fractures, some of which pass right through the samples, but many are intercepted or terminate within the rock matrix. Thus, the behavior of the core samples will be influenced not only by the properties of the rock matrix between the fractures, but also by how these macro- and micro-scale fractures mutually interact. The strain-recovery curves recorded during Leg 123 for each of the 15 basalt core samples may reflect the result of two competing time dependent processes: anelastic strain recovery and pore pressure recovery. Were these the only two processes to influence the gauge responses, then one might expect that given the additional information required, established theoretical models might be used to determine consistent stress orientations and reliable stress magnitudes. However, superimposed upon these competing processes is their respective interaction with the preexisting fractures that intersect each core. Evidence from our experiments and observations suggests that these fractures have a dominating influence on the characteristics of the recovery curves and that their effects are complex.

Electromagnetic, rock magnetic, and geochemical properties of surficial sediments in Eckernförde Bay

Submarine groundwater discharge in coastal settings can massively modify the hydraulic and geochemical conditions of the seafloor. Resulting local anomalies in the morphology and physical properties of surface sediments are usually explored with seismo-acoustic imaging techniques. Controlled source electromagnetic imaging offers an innovative dual approach to seep characterization by its ability to detect pore-water electrical conductivity, hence salinity, as well as sediment magnetic susceptibility, hence preservation or diagenetic alteration of iron oxides. The newly developed electromagnetic (EM) profiler Neridis II successfully realized this concept for a first time with a high-resolution survey of freshwater seeps in Eckernförde Bay (SW Baltic Sea). We demonstrate that EM profiling, complemented and validated by acoustic as well as sample-based rock magnetic and geochemical methods, can create a crisp and revealing fingerprint image of freshwater seepage and related reductive alteration of near-surface sediments. Our findings imply that (1) freshwater penetrates the pore space of Holocene mud sediments by both diffuse and focused advection, (2) pockmarks are marked by focused freshwater seepage, underlying sand highs, reduced mud thickness, higher porosity, fining of grain size, and anoxic conditions, (3) depletion of Fe oxides, especially magnetite, is more pervasive within pockmarks due to higher concentrations of organic and sulfidic reaction partners, and (4) freshwater advection reduces sediment magnetic susceptibility by a combination of pore-water injection (dilution) and magnetite reduction (depletion). The conductivity vs. susceptibility biplot resolves subtle lateral litho- and hydrofacies variations.

Molecular and isotopic properties of gases from ODP Holes of ODP Leg 204

We report and discuss molecular and isotopic properties of hydrate-bound gases from 55 samples and void gases from 494 samples collected during Ocean Drilling Program (ODP) Leg 204 at Hydrate Ridge offshore Oregon. Gas hydrates appear to crystallize in sediments from two end-member gas sources (deep allochthonous and in situ) as mixtures of different proportions. In an area of high gas flux at the Southern Summit of the ridge (Sites 1248-1250), shallow (0-40 m below the seafloor [mbsf]) gas hydrates are composed of mainly allochthonous mixed microbial and thermogenic methane and a small portion of thermogenic C2+ gases, which migrated vertically and laterally from as deep as 2- to 2.5-km depths. In contrast, deep (50-105 mbsf) gas hydrates at the Southern Summit (Sites 1248 and 1250) and on the flanks of the ridge (Sites 1244-1247) crystallize mainly from microbial methane and ethane generated dominantly in situ. A small contribution of allochthonous gas may also be present at sites where geologic and tectonic settings favor focused vertical gas migration from greater depth (e.g., Sites 1244 and 1245). Non-hydrocarbon gases such as CO2 and H2S are not abundant in sampled hydrates. The new gas geochemical data are inconsistent with earlier models suggesting that seafloor gas hydrates at Hydrate Ridge formed from gas derived from decomposition of deeper and older gas hydrates. Gas hydrate formation at the Southern Summit is explained by a model in which gas migrated from deep sediments, and perhaps was trapped by a gas hydrate seal at the base of the gas hydrate stability zone (GHSZ). Free gas migrated into the GHSZ when the overpressure in gas column exceeded sealing capacity of overlaying sediments, and precipitated as gas hydrate mainly within shallow sediments. The mushroom-like 3D shape of gas hydrate accumulation at the summit is possibly defined by the gas diffusion aureole surrounding the main migration conduit, the decrease of gas solubility in shallow sediment, and refocusing of gas by carbonate and gas hydrate seals near the seafloor to the crest of the local anticline structure.

Technology Choice, Change of Trade Structure, and A Case of Hungarian Economy

In the IT industry, there has been a remarkable increase in the demand for system LSI. A system LSI must be tailor-designed for each electrical appliance, and then produced. It is said that in recent years, this production method has made the IC cycle ambiguous. It can be sought that the choice of whether the economy pursues a development path centering on technology which is tradable or technology which is embodied in labor, depends on the historical background. In this paper, the economic background is explained in order to analyze and capture movements in the IT industry and technology. Then, an econometric model for Hungary has been constructed to estimate the effect of technological progress on the economy.