204 research outputs found

    Formation of a Double Diamond Cubic Phase by Thermotropic Liquid Crystalline Self-Assembly of Bundled Bolaamphiphiles

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    A quaternary amphiphile with swallow-tail side groups displays a new bicontinuous thermotropic cubic phase with symmetry Pn3‾ m and formed by two interpenetrating networks where cylindrical segments are linked by H bonds at tetrahedral junctions. Each network segment contains two bundles, each containing 12 rod-like mesogens, lying along the segment axis. This assembly leads to the first thermotropic structure of the "double diamond" type. A quantitative geometric model is proposed to explain the occurrence of this rare phase

    Helical networks of π‐conjugated rods – a robust design concept for bicontinuous cubic liquid crystalline phases with Ia3d and chiral I23 lattice

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    Bicontinuous cubic liquid crystalline phases of π‐conjugated molecules, representing self‐assembled 3D‐ordered interpenetrating networks with cubic symmetry, are receiving increasing attention due to their capacity for charge transport in all three dimensions and their inherent spontaneous helicity. Herein, a robust general design concept for creating bicontinuous cubic phases is reported. It is based on a nonsymmetric‐substituted π‐conjugated 5,5′‐diphenyl‐2,2′‐bithiophene platform with one end containing three out‐fanning flexible chains and with a range of substituents at the other end (the apex). The cubic phases are stable over broad temperature ranges, often down to ambient temperature, and tolerate a wide range of apex substitution patterns, allowing structural diversity and tailoring of the cubic phase type and application‐relevant properties. With an increasing number and size of apex substituents, a sequence of three different modes of cubic self‐assembly is observed, following an increasing helical twist. Thus, two ranges of the achiral double network Ia 3d phase range can be distinguished, a long pitch and a short pitch, with the chiral triple network I23 cubic phase in the intermediate pitch range. The findings provide a new prospect for the directed design of cubic phase‐forming functional materials based on spontaneously formed helical network liquid crystals with tunable application specific properties

    Chirality induction through nano-phase separation: Alternating network gyroid (I4132) phase by thermotropic self-assembly of X-shaped bolapolyphiles

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    The single gyroid phase as well as the alternating double network gyroid, composed of two alternating single gyroid networks, hold a significant place in ordered nanoscale morphologies for their potential applications as photonic crystals, metamaterials and templates for porous ceramics and metals. Here we report the first alternating network cubic liquid crystals. They form through self‐assembly of X‐shaped polyphiles, where the glycerol‐capped terphenyl rods lie on the gyroid surface while the semiperfluorinated and aliphatic side‐chains fill their respective separate channel networks. This new self‐assembly mode can be considered as a two‐color symmetry‐broken double gyroid morphology, providing a tailored way to fabricate novel chiral structures with sub‐10 nm periodicities using achiral compounds

    Hyaluronan Export through Plasma Membranes Depends on Concurrent K+ Efflux by Kir Channels

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    Hyaluronan is synthesized within the cytoplasm and exported into the extracellular matrix through the cell membrane of fibroblasts by the MRP5 transporter. In order to meet the law of electroneutrality, a cation is required to neutralize the emerging negative hyaluronan charges. As we previously observed an inhibiting of hyaluronan export by inhibitors of K+ channels, hyaluronan export was now analysed by simultaneously measuring membrane potential in the presence of drugs. This was done by both hyaluronan import into inside-out vesicles and by inhibition with antisense siRNA. Hyaluronan export from fibroblast was particularly inhibited by glibenclamide, ropivacain and BaCl2 which all belong to ATP-sensitive inwardly-rectifying Kir channel inhibitors. Import of hyaluronan into vesicles was activated by 150 mM KCl and this activation was abolished by ATP. siRNA for the K+ channels Kir3.4 and Kir6.2 inhibited hyaluronan export. Collectively, these results indicated that hyaluronan export depends on concurrent K+ efflux

    Transition between tangential and co-axial liquid crystalline honeycombs in the self-assembly of Y-shaped bolapolyphiles

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    p-Terphenyl based Y-shaped bolapolyphiles self-assemble into liquid crystalline honeycombs with co-axial organization of the π-conjugated rods around columns filled by alkyl sidechains. In this new hexagonal honeycomb with P6/mmm symmetry the orientation of the π-conjugated rods is perpendicular to the tangential honeycombs formed at lower temperature or with longer chain length

    Zeolite-like liquid crystals

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    Zeolites represent inorganic solid-state materials with porous structures of fascinating complexity. Recently, significant progress was made by reticular synthesis of related organic solid-state materials, such as metal-organic or covalent organic frameworks. Herein we go a step further and report the first example of a fluid honeycomb mimicking a zeolitic framework. In this unique self-assembled liquid crystalline structure, transverse-lying π-conjugated rod-like molecules form pentagonal channels, encircling larger octagonal channels, a structural motif also found in some zeolites. Additional bundles of coaxial molecules penetrate the centres of the larger channels, unreachable by chains attached to the honeycomb framework. This creates a unique fluid hybrid structure combining positive and negative anisotropies, providing the potential for tuning the directionality of anisotropic optical, electrical and magnetic properties. This work also demonstrates a new approach to complex soft-matter self-assembly, by using frustration between space filling and the entropic penalty of chain extension

    Assembling proteomics data as a prerequisite for the analysis of large scale experiments

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    <p>Abstract</p> <p>Background</p> <p>Despite the complete determination of the genome sequence of a huge number of bacteria, their proteomes remain relatively poorly defined. Beside new methods to increase the number of identified proteins new database applications are necessary to store and present results of large- scale proteomics experiments.</p> <p>Results</p> <p>In the present study, a database concept has been developed to address these issues and to offer complete information via a web interface. In our concept, the Oracle based data repository system SQL-LIMS plays the central role in the proteomics workflow and was applied to the proteomes of <it>Mycobacterium tuberculosis</it>, <it>Helicobacter pylori</it>, <it>Salmonella typhimurium </it>and protein complexes such as 20S proteasome. Technical operations of our proteomics labs were used as the standard for SQL-LIMS template creation. By means of a Java based data parser, post-processed data of different approaches, such as LC/ESI-MS, MALDI-MS and 2-D gel electrophoresis (2-DE), were stored in SQL-LIMS. A minimum set of the proteomics data were transferred in our public 2D-PAGE database using a Java based interface (Data Transfer Tool) with the requirements of the PEDRo standardization. Furthermore, the stored proteomics data were extractable out of SQL-LIMS via XML.</p> <p>Conclusion</p> <p>The Oracle based data repository system SQL-LIMS played the central role in the proteomics workflow concept. Technical operations of our proteomics labs were used as standards for SQL-LIMS templates. Using a Java based parser, post-processed data of different approaches such as LC/ESI-MS, MALDI-MS and 1-DE and 2-DE were stored in SQL-LIMS. Thus, unique data formats of different instruments were unified and stored in SQL-LIMS tables. Moreover, a unique submission identifier allowed fast access to all experimental data. This was the main advantage compared to multi software solutions, especially if personnel fluctuations are high. Moreover, large scale and high-throughput experiments must be managed in a comprehensive repository system such as SQL-LIMS, to query results in a systematic manner. On the other hand, these database systems are expensive and require at least one full time administrator and specialized lab manager. Moreover, the high technical dynamics in proteomics may cause problems to adjust new data formats. To summarize, SQL-LIMS met the requirements of proteomics data handling especially in skilled processes such as gel-electrophoresis or mass spectrometry and fulfilled the PSI standardization criteria. The data transfer into a public domain via DTT facilitated validation of proteomics data. Additionally, evaluation of mass spectra by post-processing using MS-Screener improved the reliability of mass analysis and prevented storage of data junk.</p
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