Characterization of hyperbranched glycopolymers produced in vitro using enzymes

Asymmetrical flow field flow fractionation (AF4) has proven to be a very powerful and quantitative method for the determination of the macromolecular structure of high molar mass branched biopolymers, when coupled with multi-angle laser light scattering (MALLS). This work describes a detailed investigation of the macromolecular structure of native glycogens and hyperbranched α-glucans (HBPs), with average molar mass ranging from 2?×?10⁶ to 4.3?×?10⁷ g mol^?1, which are not well fractionated by means of classical size-exclusion chromatography. HBPs were enzymatically produced from sucrose by the tandem action of an amylosucrase and a branching enzyme mimicking in vitro the elongation and branching steps involved in glycogen biosynthesis. Size and molar mass distributions were studied by AF4, coupled with online quasi-elastic light scattering (QELS) and transmission electron microscopy. AF4-MALLS-QELS has shown a remarkable agreement between hydrodynamic radii obtained by online QELS and by AF4 theory in normal mode with constant cross flow. Molar mass, size, and dispersity were shown to significantly increase with initial sucrose concentration, and to decrease when the branching enzyme activity increases. Several populations with different size range were observed: the amount of small size molecules decreasing with increasing sucrose concentration. The spherical and dense global conformation thus highlighted was partly similar to native glycogens. A more detailed study of HBPs synthesized from low and high initial sucrose concentrations was performed using complementary enzymatic hydrolysis of external chains and chromatography. It emphasized a more homogeneous branching pattern than native glycogens with a denser core and shorter external chains.

Axial Elongation of Mononuclear Lanthanide Metallocenophanes: Magnetic Properties of Dysprosium‐ and Terbium‐[1]Ruthenocenophane Complexes

We report the first f‐block‐ruthenocenophane complexes 1 (Dy) and 2 (Tb) and provide a comparative discussion of their magnetic structure with respect to earlier reported ferrocenophane analogues. While axial elongation of the rare trigonal‐prismatic geometry stabilizes the magnetic ground state in the case of Dy³⁺ and results in a larger barrier to magnetization reversal (U), a decrease in U is observed for the case of Tb³⁺.     

A Dual Threat: Redox‐Activity and Electronic Structures of Well‐Defined Donor–Acceptor Fulleretic Covalent‐Organic Materials

The effect of donor (D)–acceptor (A) alignment on the materials electronic structure was probed for the first time using novel purely organic porous crystalline materials with covalently bound two‐ and three‐dimensional acceptors. The first studies towards estimation of charge transfer rates as a function of acceptor stacking are in line with the experimentally observed drastic, eight‐fold conductivity enhancement. The first evaluation of redox behavior of buckyball‐ or tetracyanoquinodimethane‐integrated crystalline was conducted. In parallel with tailoring the D‐A alignment responsible for “static” changes in materials properties, an external stimulus was applied for “dynamic” control of the electronic profiles. Overall, the presented D–A strategic design, with stimuli‐controlled electronic behavior, redox activity, and modularity could be used as a blueprint for the development of electroactive and conductive multidimensional and multifunctional crystalline porous materials.     

Role of the morphology and polyphosphate in Trichoderma harzianum related to cadmium removal

This study concerns the metabolism of polyphosphate in Trichoderma harzianum, a biocontrol agent with innate resistance against most chemicals used in agriculture, including metals, when grown in the presence of different concentrations of cadmium. The biomass production was affected by the concentration of metal used. Control cultures were able to accumulate polyphosphate under the conditions used. Moreover, the presence of cadmium induced a reduction in polyphosphate content related to the concentration used. The morphological/ultrastructural aspects were characterized by using optical and scanning electron microscopy, and were affected by the heavy metal presence and concentration. The efficiency of cadmium removal revealed the potential of the microorganism for use in remediation. The data indicate the potential for polyphosphate accumulation by the fungus, as well as its degradation related to tolerance/survival in the presence of cadmium ions.     

Simulation and high-precision wavelength determination of?noisy?2D Fabry–Pérot interferometric rings for direct-detection Doppler?lidar and laser spectroscopy

Doppler wind lidar (DWL) measurements by the fringe-imaging technique in front of aircrafts at flight speed require rapid processing of backscattered signals. We discuss the measurement principle to derive the 3D wind vector from three line-of-sight (LOS) measurements. Then we simulate realistic fringe patterns of a Fabry–Pérot-interferometer (FPI) on a 2D charge-coupled device (CCD) localized at the focal plane behind it, taking atmospheric and instrument properties like scattering and noise into account. A laser at 355 nm with pulse energies of 70 mJ at 100 Hz repetition rate and a range bin of only 10 m were assumed. This yields count rates of 24 (13) million photons per pulse at 56 (76) m distance and 8.5 km altitude that are distributed on a CCD with up to 960×780 pixels without intensification and therefore generate noisy pixel signals. We present two methods for the precise determination of the radii, i.e., wavelengths of these simulated FPI rings and show that both are suitable for eliminating pixel noise from the output and coping with fringe broadening by Rayleigh scattering. One of them proves to reach the accuracy necessary for LOS velocity measurements. A standard deviation of 2.5 m/s including center determination can be achieved with only 20 images to average. The bias is 7 m/s. For exactly known ring centers, each can be even better than 2 m/s. The methods could also be useful for high-resolution laser spectroscopy.     

Non-affine strain measures for continuum models of network materials

Based on stretch averaging, two non-affine strain measures for materials with random network microstructure are suggested. The first concept provides a scaling between affine and non-affine behaviour that is predefined by the network functionality. The second approach applies to fibres that experience strong reorientation upon macroscopic deformation of the network. (© 2014 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim)     

Dual-photoelectrode photoelectrochemical cell exploiting a photoanode based on cadmium sulfide and anatase TiO2 photocatalysts for tannic acid detection

Journal of Solid State Electrochemistry - Photoelectrochemical systems based on half-photoelectrochemical cells have been widely exploited in the development of analytical methods. However, the...     

Axial Elongation of Mononuclear Lanthanide Metallocenophanes: Magnetic Properties of Dysprosium- and Terbium-[1]Ruthenocenophane Complexes

We report the first f-block-ruthenocenophane complexes 1 (Dy) and 2 (Tb) and provide a comparative discussion of their magnetic structure with respect to earlier reported ferrocenophane analogues. While axial elongation of the rare trigonal-prismatic geometry stabilizes the magnetic ground state in the case of Dy³⁺ and results in a larger barrier to magnetization reversal (U), a decrease in U is observed for the case of Tb³⁺.