Local estradiol metabolism in osteoblast- and osteoclast-like cells

Bone is an estradiol-responsive tissue. Estrogen withdrawal during the menopause causes loss of bone mass and clinically relevant osteoporosis in a third of all women. Sufficient or impaired local production, as well as degradation of estradiol in cells present in the bone microenvironment might be an important mechanism of rescue or might contribute to the development of osteoporosis, respectively. We therefore investigated aromatase and 17beta-hydroxysteroid dehydrogenase type IV (17beta-HSD IV) expression in osteoblast- and osteoclast-like cells. Aromatase mRNA was increasingly expressed in myeloid THP 1 cells differentiated along the monocyte/phagocyte pathway exploiting vitamin D and either granulocyte-macrophage-stimulating factor (GMCSF) or macrophage-stimulating factor (MCSF). In long-term cultures, when sequentially exposed to vitamin D (days 0-21) and GMCSF (days 5-10) and plated on collagen, the amount of expression of aromatase mRNA steadily increased along with the increasing expression of osteopontin mRNA, alpha(v) integrin mRNA, c-fms (MCSF-receptor) mRNA and multinucleated cells developing. The conversion of estradiol from testosterone (10(-7) M/l) in the supernatants of dishes mirrored changes in aromatase mRNA expression and by day 21 rose to 30,000 ng/10(7) cells/24 h. 17Beta-HSD IV mRNA expression was abundant in undifferentiated THP 1 cells and was decreased to approximately 50% by day 21. Unstimulated SV-40 immortalized fetal osteoblasts did not express aromatase mRNA, but the expression was stimulated by the addition of the phorbol ester phorbol myristate acetate (PMA). Unstimulated osteoblasts from primary cultures did not express aromatase mRNA. Osteoblast-like osteosarcoma cells MG 63 expressed faint levels of aromatase mRNA in contrast to the osteosarcoma cell line HOS 58. 17Beta-HSD IV mRNA was expressed in fetal osteoblasts as well as in osteoblasts from primary culture, MG 63 and HOS 58 cells. In summary, we can show the expression of estradiol metabolizing enzymes in cells which are present in the bone microenvironment. Impaired aromatase expression and/or enhanced expression of 17beta-HSD IV may contribute to the pathogenesis of osteoporosis.     

Imaging lung function using rapid dynamic acquisition of <Emphasis Type="Italic">T</Emphasis><Subscript>1</Subscript>-maps during oxygen enhancement

This paper describes imaging of lung function with oxygen-enhanced MRI using dynamically acquired T ₁ parameter maps, which allows an accurate, quantitative assessment of time constants of T ₁-enhancement and therefore lung function. Eight healthy volunteers were examined on a 1.5-T whole-body scanner. Lung T ₁-maps based on an IR Snapshot FLASH technique (TE = 1.4 ms, TR = 3.5 ms, FA = 7 ^∘) were dynamically acquired from each subject. Without waiting for full relaxation between subsequent acquisition of T ₁-maps, one T ₁-map was acquired every 6.7 s. For comparison, all subjects underwent a standard pulmonary function test (PFT). Oxygen wash-in and wash-out time course curves of T ₁ relaxation rate (R ₁)-enhancement were obtained and time constants of oxygen wash-in (w _in) and wash-out (w _out) were calculated. Averaged over the whole right lung, the mean w _out was 43.90 ± 10.47 s and the mean (w _in) was 51.20 ± 15.53 s, thus about 17% higher in magnitude. Wash-in time constants correlated strongly with forced expired volume in one second in percentage of the vital capacity (FEV₁ % VC) and with maximum expiratory flow at 25% vital capacity (MEF25), whereas wash-out time constants showed only weak correlation. Using oxygen-enhanced rapid dynamic acquisition of T ₁-maps, time course curves of R ₁-enhancement can be obtained. With w _in and w _out two new parameters for assessing lung function are available. Therefore, the proposed method has the potential to provide regional information of pulmonary function in various lung diseases.     

Virtually Bare Nanocrystal Surfaces: Significantly Enhanced Electrical Transport in CuInSe2 and CuIn1−xGaxSe2 Thin Films upon Ligand Exchange with Thermally Degradable 1‐Ethyl‐5‐Thiotetrazole

A facile and safe ligand exchange method for readily synthesized CuInSe₂ (CIS) and CuIn_1‐xGa_xSe₂ (CIGS) nanocrystals (NCs) from oleylamine to 1‐ethyl‐5‐thiotetrazole, preserving the colloidal stability of the chalcopyrite structure, is presented. 1‐Ethyl‐5‐thiotetrazole as thermally degradable ligand is adapted for the first time for trigonal pyramidal CIS (18 nm), elongated CIS (9 nm) and CIGS NCs (6 nm). Exchanged NC solutions are processed onto gold electrodes yielding ordered thin films. These films are thermally annealed at 260 °C to completely remove 1‐ethyl‐5‐thiotetrazol leaving individual closely assembled NCs with virtually bare surfaces. The current–voltage characteristics of the NC solids are measured prior to ligand thermolysis in the dark and under illumination and after ligand thermolysis in the same manner. The conductivity of trigonal pyramidal CIS increases by four orders of magnitude (1.4 × 10^?9 S cm^?1 (dark) to 1.4 × 10^?5 S cm^?1 (illuminated)) for ligand‐free NC films. Elongated CIS NC films show a three orders of magnitude conductivity increase and CIGS NC films exhibit improved conductivity by two orders of magnitude. Conductivity enhancement thereby depends on the NC size accentuating the role of trap‐states and internal grain boundaries in ligand‐free NC solids for electrical transport. This approach for the first time offers the possibility to address chalcopyrite materials’ electrical properties in a virtually ligand‐free state.     

Double refraction of a Gaussian beam into a uniaxial crystal

For a linearly polarized three-dimensional Gaussian beam in air that is normally incident upon a plane interface with a uniaxial crystal with optic axis in an arbitrary direction, we present integral representations for the transmitted field suitable for asymptotic analysis and efficient numerical evaluation and derive analytical expressions for transmitted nontruncated Gaussian beams for the cases in which the incident beam is polarized parallel to the plane containing the optic axis and the interface normal and transverse to it. The general solution for an arbitrary polarization state of an incident Gaussian beam follows by superposition of these two solutions.     

Investigation of the Photocatalytic Hydrogen Production of Semiconductor Nanocrystal-Based Hydrogels

Destabilization of a ligand-stabilized semiconductor nanocrystal solution with an oxidizing agent can lead to a macroscopic highly porous self-supporting nanocrystal network entitled hydrogel, with good accessibility to the surface. The previously reported charge carrier delocalization beyond a single nanocrystal building block in such gels can extend the charge carrier mobility and make a photocatalytic reaction more probable. The synthesis of ligand-stabilized nanocrystals with specific physicochemical properties is possible, thanks to the advances in colloid chemistry made in the last decades. Combining the properties of these nanocrystals with the advantages of nanocrystal-based hydrogels will lead to novel materials with optimized photocatalytic properties. This work demonstrates that CdSe quantum dots, CdS nanorods, and CdSe/CdS dot-in-rod-shaped nanorods as nanocrystal-based hydrogels can exhibit a much higher hydrogen production rate compared to their ligand-stabilized nanocrystal solutions. The gel synthesis through controlled destabilization by ligand oxidation preserves the high surface-to-volume ratio, ensures the accessible surface area even in hole-trapping solutions and facilitates photocatalytic hydrogen production without a co-catalyst. Especially with such self-supporting networks of nanocrystals, the problem of colloidal (in)stability in photocatalysis is circumvented. X-ray photoelectron spectroscopy and photoelectrochemical measurements reveal the advantageous properties of the 3D networks for application in photocatalytic hydrogen production.     

Isotope-Guided Metabolomics Reveals Divergent Incorporation of Valine into Different Flavor Precursor Classes in Chives

Plants of the genus Allium such as chives, onions or garlic produce S-alk(en)yl cysteine sulfoxides as flavor precursors. Two major representatives are S-propenyl cysteine sulfoxide (isoalliin) and S-propyl cysteine sulfoxide (propiin), which only differ by a double bond in the C₃ side chain. The propenyl group of isoalliin is derived from the amino acid valine, but the source of the propyl group of propiin remains unclear. Here, we present an untargeted metabolomics approach in seedlings of chives (Allium schoenoprasum) to track mass features containing sulfur and/or ¹³C from labeling experiments with valine-¹³C₅ guided by their isotope signatures. Our data show that propiin and related propyl-bearing metabolites incorporate carbon derived from valine-¹³C₅, but to a much lesser extent than isoalliin and related propenyl compounds. Our findings provide new insights into the biosynthetic pathways of flavor precursors in Allium species and open new avenues for future untargeted labeling experiments.     

Micro-Cup Architecture for Printing and Coating Asymmetric 2d-Material-Based Solid-State Supercapacitors

High energy density micro-supercapacitors (MSCs) are in high demand for miniaturized electronics and microsystems. Research efforts today focus on materials development, applied in the planar interdigitated, symmetric electrode architecture. A novel “cup & core” device architecture that allows for printing of asymmetric devices without the need of accurately positioning the second finger electrode here have been introduced. The bottom electrode is either produced by laser ablation of a blade-coated graphene layer or directly screen-printed with graphene inks to create grids with high aspect ratio walls forming an array of “micro-cups”. A quasi-solid-state ionic liquid electrolyte is spray-deposited on the walls; the top electrode material -MXene inks- is then spray-coated to fill the cup structure. The architecture combines the advantages of interdigitated electrodes for facilitated ion-diffusion, which is critical for 2D-material-based energy storage systems by providing vertical interfaces with the layer-by-layer processing of the sandwich geometry. Compared to flat reference devices, volumetric capacitance of printed “micro-cups” MSC increased considerably, while the time constant decreased (by 58%). Importantly, the high energy density (3.99 µWh cm⁻²) of the “micro-cups” MSC is also superior to other reported MXene and graphene-based MSCs.     

Enabling Technologies in Carbohydrate Chemistry: Automated Glycan Assembly,Flow Chemistry and Data Science

The synthesis of defined oligosaccharides is a complex task. Several enabling technologies have been introduced in the last two decades to facilitate synthetic access to these valuable biomolecules. In this concept, we describe the technological solutions that have advanced glycochemistry using automated glycan assembly, flow chemistry and data science as examples. We highlight how the synergies between these different technologies can further advance the field, with progress toward the realization of a self-driving lab for glycan synthesis.     

Lipid modification of amino acids,carbohydrates and polyols

Agricultural crops provide a considerable reservoir of useful and low cost raw materials like fats and oils, plant proteins and carbohydrates. By selective combination of their molecular constituents (e. g. fatty acids, glycerol, amino acids, saccharides), a wide variety of surface active materials can be prepared. Due to their molecular constitution, all of them are potentially biodegradable. In this article we describe two generally applicable methods for the synthesis of such combination products using fatty acids from plant oils – one of the most important renewable materials as feedstock for the chemical industry – in combination with amino acids and monosaccharides including sugar alcohols. Using the high selectivities displayed by lipases, which catalyze a wide variety of transformations under very mild conditions (pH, temperature) with high atom efficiency in various non‐toxic solvents and without the production of by‐products or waste, numerous useful products can be obtained ranging all the way from surface active compounds (detergents and emulsifiers for food and personal care products) such as mono‐ and diglycerides, sugar esters, synthetic building blocks, products for food and dietary applications, all the way to novel methods for the production of biofuels (biodiesel). In our continuing effort to devise novel and generally applicable methods for the syntheses of such combination products we recently discovered a novel class of building blocks, fatty acid modified anhydrides of hydroxy carboxylic acids such as citric acid, tartaric acid and malic acid which led to alternative synthetic approaches towards new classes of the title compounds.     

Parallel integration of aligned carbon strings in polymer composite: Dielectrophoretic preparation,finite element simulation,and electrical characterization

We report on dielectrophoretic alignment of carbon black particles into radially arranged string‐like assemblies in oligourethane mixtures followed by photopolymerization. Using finite element modelling and optical microscopy we find significant difference in field distributions depending on the substrate beneath aligned films. On glass, the field is concentrated between the electrode tips leading to string‐like assemblies between the tips. On oxide covered silicon, the field is distributed along the electrode circumference leading to more distributed fractal assemblies. Using comprehensive dc resistance measurements and ac‐impedance spectroscopy we show that the resistance of the strings varies from 120 kΩ to 5 MΩ with a mean of 1.03 MΩ. Strings on oxide covered silicon show significantly higher resistances than the strings on glass. We also demonstrate the effect of aging and an increase in resistance through elongating aligned strings. POLYM. COMPOS., 36:1866–1874, 2015. © 2014 Society of Plastics Engineers