Synthesis and Photochromic Properties of Configurationally Varied Azobenzene Glycosides

Spatial orientation of carbohydrates is a meaningful parameter in carbohydrate recognition processes. To vary orientation of sugars with temporal and spatial resolution, photosensitive glycoconjugates with favorable photochromic properties appear to be opportune. Here, a series of azobenzene glycosides were synthesized, employing glycoside synthesis and Mills reaction, to allow “switching” of carbohydrate orientation by reversible E/Z isomerization of the azobenzene N=N double bond. Their photochromic properties were tested and effects of azobenzene substitution as well as the effect of anomeric configuration and the orientation of the sugars 2-hydroxy group were evaluated.     

Electronic transport in graphene nanostructures on SiO2

We report two experiments on graphene nanostructures. The first was performed on a graphene nanoribbon, where the nature of electronic transport was investigated in detail. Electrons or holes are found to localize in pockets of the potential along the ribbon. Transport is governed by the joint action of localization and Coulomb interaction. The temperature-dependence of the conductance shows activated behavior at temperatures above a few Kelvin. The activation energy retraces the edges of Coulomb blockade diamonds found in nonlinear transport. In the second experiment the metallic tip of a low-temperature scanning force microscope was scanned above a graphene quantum dot. In addition to the familiar Coulomb blockade fringes, localized states are detected forming in the constrictions connecting the dot to source and drain.     

Fabrication of three-dimensional photonic crystals with tunable photonic properties by biotemplating

Photonic crystals with tunable D-surface structures for possible high-temperature gas- and temperature-sensing applications were prepared by a biotemplating method. This included infiltrating colored scales of the beetle Entimus imperialis with an organopolysiloxane mixture followed by simultaneous combustion of the template and calcination of the cured organopolysiloxane. A high-yield inorganic silica-based replica of the original structure was obtained, which is capable of withstanding temperatures up to 600 °C. Light- and scanning electron microscopy combined with focused ion beam milling showed a precise replication of the whole scales and their internal D-surface structure. Fourier-transform infrared spectroscopy and X-ray diffraction analysis confirmed the complete curing of the organopolysiloxanes and their transformation into amorphous silica during calcination. The dielectric constant of the manufactured materials determined by Abbé refractometry was ? = 2.3180 and used to perform band structure calculations utilizing the plane wave expansion method. By changing the chain length and degree of crosslinking of the organopolysiloxane precursor mixture, the lattice parameters and filling factors, and therefore the photonic properties of the replicas, could be tuned.     

Resorcinol‐based benzoxazine with low polymerization temperature

The industrial applications of benzoxazines are limited due to their high curing temperatures. This drawback can be overcome by more reactive precursor compared to conventional benzoxazines or by application of efficient initiators. We report the synthesis of a new resorcinol‐based benzoxazine and its cationic polymerization with thermolatent super acids, namely organic sulfonium hexafluoroantimonates. This combination of a reactive precursor and an efficient initiator results in a curing temperature below 100 °C (differential scanning calorimetry onset) which is up to now one of the lowest polymerization temperatures for benzoxazine systems. Furthermore, the thermal stability of the formed polybenzoxazine has not been influenced by the applied initiators. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 1693–1699     

Robust multilevel methods for quadratic finite element anisotropic elliptic problems

This paper discusses a class of multilevel preconditioners based on approximate block factorization for conforming finite element methods employing quadratic trial and test functions. The main focus is on diffusion problems governed by a scalar elliptic partial differential equation with a strongly anisotropic coefficient tensor. The proposed method provides a high robustness with respect to non‐grid‐aligned anisotropy, which is achieved by the interaction of the following components: (i) an additive Schur complement approximation to construct the coarse‐grid operator; (ii) a global block (Jacobi or Gauss–Seidel) smoother complementing the coarse‐grid correction based on (i); and (iii) utilization of an augmented coarse grid, which enhances the efficiency of the interplay between (i) and (ii). The performed analysis indicates the high robustness of the resulting two‐level method. Moreover, numerical tests with a nonlinear algebraic multilevel iteration method demonstrate that the presented two‐level method can be applied successfully in the recursive construction of uniform multilevel preconditioners of optimal or nearly optimal order of computational complexity. Copyright © 2013 John Wiley & Sons, Ltd.     

Brodie's or Hummers’ Method: Oxidation Conditions Determine the Structure of Graphene Oxide

Synthesis and studies of graphite oxide started more than 150 years ago and turned into a boom by the measurements of the outstanding physical properties of graphene. A series of preparation protocols emanated trying to optimize the synthesis of graphene oxide in order to obtain a less defective material, as source for graphene. However, over-oxidation of the carbon framework hampered establishing structure-property relationships. Here, the fact that two different synthetic methods for graphene oxide preparation lead to very similar types of graphene oxide with a preserved graphene lattice is demonstrated. Either sodium chlorate in nitric acid (similar to Brodie's method) or potassium permanganate in sulfuric acid (similar to Hummers’ method) treatment are possible; however, reaction conditions must be controlled. With a preserved carbon lattice analytical differences between the samples relate to the altered on-plane functionality. Consequently, terming preparation protocols “according to Brodie's/Hummers’ method” is not sufficient.     

A tin-containing liquid crystalline polymer with two glass temperatures

A tin-containing liquid crystalline side group polymer was synthesized and characterized. Two glass transitions were detected by calorimetric investigations. The X-ray pattern corresponds to a smectic C order of the side groups and a disordered isotropic main chain. Dielectric measurements show two relaxation ranges which are influenced by the glass transitions and a fast local process. The low frequency mechanism can be related to the reorientation of the side groups and the higher glass transition temperature. The second is connected with the α-relaxation of the main chain and freezes in at lower temperatures.     

Efficient Entropy-Driven Inhibition of Dipeptidyl Peptidase III by Hydroxyethylene Transition-State Peptidomimetics

Dipeptidyl peptidase III (DPP3) is a ubiquitously expressed Zn-dependent protease, which plays an important role in regulating endogenous peptide hormones, such as enkephalins or angiotensins. In previous biophysical studies, it could be shown that substrate binding is driven by a large entropic contribution due to the release of water molecules from the closing binding cleft. Here, the design, synthesis and biophysical characterization of peptidomimetic inhibitors is reported, using for the first time an hydroxyethylene transition-state mimetic for a metalloprotease. Efficient routes for the synthesis of both stereoisomers of the pseudopeptide core were developed, which allowed the synthesis of peptidomimetic inhibitors mimicking the VVYPW-motif of tynorphin. The best inhibitors inhibit DPP3 in the low μM range. Biophysical characterization by means of ITC measurement and X-ray crystallography confirm the unusual entropy-driven mode of binding. Stability assays demonstrated the desired stability of these inhibitors, which efficiently inhibited DPP3 in mouse brain homogenate.     

Polyampholytic Graft Copolymers as Matrix for TiO2/Eosin Y/[Mo3S13]2− Hybrid Materials and Light-Driven Catalysis

An effective strategy to enhance the performance of inorganic semiconductors is moving towards organic-inorganic hybrid materials. Here, we report the design of core–shell hybrid materials based on a TiO₂ core functionalized with a polyampholytic (poly(dehydroalanine)-graft-(n-propyl phosphonic acid acrylamide) shell (PDha-g-PAA@TiO₂). The PDha-g-PAA shell facilitates the efficient immobilization of the photosensitizer Eosin Y (EY) and enables electronic interactions between EY and the TiO₂ core. This resulted in high visible-light-driven H₂ generation. The enhanced light-driven catalytic activity is attributed to the unique core–shell design with the graft copolymer acting as bridge and facilitating electron and proton transfer, thereby also preventing the degradation of EY. Further catalytic enhancement of PDha-g-PAA@TiO₂ was possible by introducing [Mo₃S₁₃]²⁻ cluster anions as hydrogen-evolution cocatalyst. This novel design approach is an example for a multi-component system in which reactivity can in future be independently tuned by selection of the desired molecular or polymeric species.     

Zeta-potential measurements of OTS-covered silica samples

We have carried out zeta-potential measurements on two different OTS (octadecyl-trichlorosilane)-covered silicas (fused silica, quartz 0001) prepared under identical conditions. Streaming current measurements on the fused silica supported OTS sample indicate a well reproducible IEP of 3.5. The major part of the study focused on the quartz 0001 supported sample with an IEP lower than that of the fused silica support and in agreement with that found in a spectroscopic study. The IEP in water (on addition of HCl) was found at around pH 3, and appeared to shift to lower values in three subsequent measurements. A final measurement after a separate series in KCl media gave the same IEP as obtained in the very first measurement, suggesting that the experiments did not significantly change the interfacial properties despite a large number of experiments. In one series of measurements care was taken to exclude any cations other than protons from the measurements, such that protons are the only counter-ions to the negative net charge. While our IEPs with the quartz support agree well with recent estimates from sum frequency generation (SFG) investigations, none of the zeta-potential vs pH curves would mimic a pattern experimentally observed in the amplitude of the “ice-like” water band between pH 3.5 and 5 in that SFG study. Furthermore, our results do not indicate any significant chloride-ion adsorption in KCl systems, but instead the shift of the IEP with increasing KCl to higher pH values rather indicates specific effects of potassium ions. Under conditions more relevant to the spectroscopic study (i.e. in absence of potassium) no specific pattern reminiscent of the SFG results was found. When tested it was found that surface conductivity was negligible.