Molecular Regulation of Copper Homeostasis in the Male Gonad during the Process of Spermatogenesis

Owing to its redox properties, copper is a cofactor of enzymes that catalyze reactions in fundamental metabolic processes. However, copper–oxygen interaction, which is a source of toxic oxygen radicals generated by the Fenton reaction, makes copper a doubled-edged-sword in an oxygen environment. Among the microelements influencing male fertility, copper plays a special role because both copper deficiency and overload in the gonads worsen spermatozoa quality and disturb reproductive function in mammals. Male gametes are produced during spermatogenesis, a multi-step process that consumes large amounts of oxygen. Germ cells containing a high amount of unsaturated fatty acids in their membranes are particularly vulnerable to excess copper-mediated oxidative stress. In addition, an appropriate copper level is necessary to initiate meiosis in premeiotic germ cells. The balance between essential and toxic copper concentrations in germ cells at different stages of spermatogenesis and in Sertoli cells that support their development is handled by a network of copper importers, chaperones, recipient proteins, and exporters. Here, we describe coordinated regulation/functioning of copper-binding proteins expressed in germ and Sertoli cells with special emphasis on copper transporters, copper transporting ATPases, and SOD1, a copper-dependent antioxidant enzyme. These and other proteins assure copper bioavailability in germ cells and protection against copper toxicity.     

Antimony substituted lanthanum orthoniobate proton conductor – Structure and electronic properties

X-ray and neutron diffraction have been utilized to analyze the crystalline and electronic structure of lanthanum orthoniobate substituted by antimony. Using X-ray absorption spectroscopy and photoelectron spectroscopy, changes in the electronic structure of the material upon substitution have been analyzed. The structural transition temperature between fergusonite and scheelite phases for 30 mol% antimony substitution was found to be 15°C. Based on the neutron data, the oxygen nonstoichiometry was found to be relatively low. Moreover no influence on the position of the valence band maximum was observed. The influence of the protonation on the electronic structure of constituent oxides has been studied. Absorption data show that the incorporation of protonic defects into the lanthanum orthoniobate structure leads to changes in lanthanum electronic structure and a decrease in the density of unoccupied electronic states.     

Compatibility of Distinct Label-Free Proteomic Workflows in Absolute Quantification of Proteins Linked to the Oocyte Quality in Human Follicular Fluid

We present two separate label-free quantitative workflows based on different high-resolution mass spectrometers and LC setups, which are termed after the utilized instrument: Quad-Orbitrap (nano-LC) and Triple Quad-TOF (micro-LC) and their directed adaptation toward the analysis of human follicular fluid proteome. We identified about 1000 proteins in each distinct workflow using various sample preparation methods. With assistance of the Total Protein Approach, we were able to obtain absolute protein concentrations for each workflow. In a pilot study of twenty samples linked to diverse oocyte quality status from four donors, 455 and 215 proteins were quantified by the Quad-Orbitrap and Triple Quad-TOF workflows, respectively. The concentration values obtained from both workflows correlated to a significant degree. We found reasonable agreement of both workflows in protein fold changes between tested groups, resulting in unified lists of 20 and 22 proteins linked to oocyte maturity and blastocyst development, respectively. The Quad-Orbitrap workflow was best suited for an in-depth analysis without the need of extensive fractionation, especially of low abundant proteome, whereas the Triple Quad-TOF workflow allowed a more robust approach with a greater potential to increase in effectiveness with the growing number of analyzed samples after the initial effort of building a comprehensive spectral library.     

Metallated conjugated polymers as a new avenue towards high-efficiency polymer solar cells

Bulk heterojunction solar cells have been extensively studied owing to their great potential for cost-effective photovoltaic devices. Although recent advances resulted in the fabrication of poly(3-hexylthiophene) (P3HT)/fullerene derivative based solar cells with efficiencies in the range 4.4-5.0%, theoretical calculations predict that the development of novel donor materials with a lower bandgap is required to exceed the power-conversion efficiency of 10%. However, all of the lower bandgap polymers developed so far have failed to reach the efficiency of P3HT-based cells. To address this issue, we synthesized a soluble, intensely coloured platinum metallopolyyne with a low bandgap of 1.85 eV. The solar cells, containing metallopolyyne/fullerene derivative blends as the photoactive material, showed a power-conversion efficiency with an average of 4.1%, without annealing or the use of spacer layers needed to achieve comparable efficiency with P3HT. This clearly demonstrates the potential of metallated conjugated polymers for efficient photovoltaic devices.     

Fabrication of nanoplasmonic arrays with square symmetry using spin-coating method

A spin-coating method was applied for the first time to prepare a colloid monolayer on the optical crossed gratings used as a template. Four polystyrene colloids of various nominal sizes and different surface charges were spin-coated on templates with periods matched to the particles size. Three types of coverage were described depending on the spin-coating parameters and particles type. The optimal coverage was obtained for all four particles sizes. A way of finding the right spin-coating parameters was proposed. The analysis of a coverage capability of polystyrene particles showed that neutral particles have the highest ability to order on the templates used. Large monolayered areas of ordered particles were used as a lithographic mask for generating a pattern of gold nanoparticles with a square symmetry. A few hundred square micrometers large, continuous and fully defect-free areas of gold nanoparticles were produced on the nearly entire surface of the templated substrates.     

TiCp*(OMe)3 versus Ti(OMe)4 in atomic layer deposition of TiO2 with water--ab initio modelling of atomic layer deposition surface reactions

It is a common finding that titanocene-derived precursors do not yield TiO2 films in ALD with water. For instance, ALD with Ti(OMe)4 and water gives 0.5 A/cycle, while TiCp*(OMe)3 does not show any growth (Me=CH3, Cp* = C5(CH3)5). This is apparently in contradiction with the computed reactivity of the ligands: the energetics of hydrolysis of the gas-phase precursor indicate that TiCp*(OMe)3 is more reactive to ligand elimination than Ti(OMe)4. However such a model of precursor reactivity neglects surface reactions such as adsorption, diffusion and desorption, all of which can have an important effect on ALD growth rate. A more accurate model of the surface reaction is needed to find the reason for the different behaviours of Ti(OMe)4 and TiCp*(OMe)3 in the ALD process. The more realistic surface model is a TiO2 slab that is periodic in three dimensions. These calculations reveal that TiCp*(OMe)3 does not chemisorb in the usual way because of extreme crowding of the Ti centre by Cp* and that this prevents ALD growth.     

Indium tin oxide nanorod electrodes for polymer photovoltaics

We have deposited indium tin oxide (ITO) nanorods on glass and glass/ITO substrates by DC sputtering and by e-beam deposition. The properties of the nanorods deposited by different methods and on different substrates have been investigated. The ITO nanorods were also used as an electrode in bulk heterojunction polymer solar cells. We found that the nanorod morphology and sheet resistance had a significant effect on the solar cell performance, with significant improvements in the efficiency compared to commercial ITO film substrates in all cases except for e-beam deposited nanorods on glass that had high sheet resistance. The best power conversion efficiency achieved was 3.2 % (for sputtered ITO nanorods on ITO), compared to 2.1 % for commercial ITO substrates.     

Augmented Lagrangian based reconstruction of non-uniformly sub-Nyquist sampled MRI data

MRI has recently been identified as a promising application for compressed-sensing-like regularization because of its potential to speed up the acquisition while maintaining the image quality. Thereby non-uniform k-space trajectories, such as random or spiral trajectories, are becoming more and more important, because they are well suited to be used within the compressed-sensing (CS) acquisition framework. In this paper, we propose a new reconstruction technique for non-uniformly sub-Nyquist sampled k-space data. Several parts make up this technique, such as the non-uniform Fourier transform (NUFT), the discrete shearlet transform and a augmented Lagrangian based optimization algorithm. Because MRI images are real-valued, we introduce a new imaginary value suppressing prior, which attenuates imaginary components of MRI images during reconstruction, resulting in a better overall image quality. Further, a preconditioning based on the Voronoi cell size of each NUFT data point speeds up the conjugate gradient optimization used as part of the optimization algorithm. The resulting algorithm converges in a relatively small number of iterations and guarantees solutions that fully comply to the imposed constraints. The results show that the algorithm is applicable not only to sub-Nyquist sampled k-space reconstruction, but also to MR image fusion and/or resolution enhancement.     

Performance analysis of dual switched diversity over correlated Weibull fading channels with co‐channel interference

This paper studies the performance of switch and stay combining (SSC) diversity in the presence of co‐channel interference over correlated Weibull fading channels. SSC diversity based on signal‐to‐interference ratio (SIR) is a low‐complexity and a very efficient technique that reduces fading and co‐channel interference influence. New closed‐form expressions for the probability density function and cumulative distribution function of the output SIR's are derived. These formulas are used in a detailed analysis of the average output SIR and outage probability. The influence of fading severity and correlation coefficient on the optimum switching threshold and system performance is investigated. Monte Carlo simulations are performed to verify obtained theoretical results and determine average bit error rate in detecting binary phase‐shift keying (BPSK), differential BPSK and quadrature amplitude modulation signals. Copyright © 2011 John Wiley & Sons, Ltd.     

Quality assessment of gluten-free crackers based on buckwheat flour

Formulation and characterization of new products - gluten-free crackers based on two types of buckwheat flour (refined and wholegrain) are presented in this study. Their proximate composition, content of main antioxidant compounds (polyphenols and tocopherols), antioxidant activity (radical scavenging activity on 1,1-diphenyl-2-picrylhydrazyl radicals - DPPH) and sensory quality were analyzed and compared with those of wheat crackers made from refined and wholegrain wheat flours.Protocatechuic acid and ferulic acid were quantified in buckwheat and wheat crackers, while two flavonoids, rutin and quercetin, were quantified only in buckwheat crackers. Content of total phenolics and tocopherols was significantly higher (P < 0.05) in buckwheat crackers in comparison to wheat crackers. Tocopherols in crackers were present in the following order: α- ? γ- > δ-tocopherol. Buckwheat crackers exhibited significantly higher (P < 0.05) radical scavenging activity on DPPH according to their IC₅₀ values.No significant differences were observed in sensory quality of wholegrain buckwheat crackers in comparison to wheat ones. Crackers made from buckwheat flours can broaden the utilization of buckwheat, increase supply of gluten-free products on the market and may be regarded as health-promoting functional foods, especially for celiac disease patients.