We have examined the H2O2-dependent oxidative dehalogenation of 2,4,6-trihalophenols and p-halophenols catalyzed by Caldariomyces fumago chloroperoxidase (CCPO). CCPO is significantly more robust than other peroxidases and can function under harsher reaction conditions, and so its ability to dehalogenate halophenols could lead to its use as a bioremediation catalyst for aromatic dehalogenation reactions. Optimal catalysis occurred under acidic conditions (100 mM potassium phosphate solution, pH 3.0). UV-visible absorption spectroscopy, high-performance liquid chromatography, and gas chromatography/mass spectrometry clearly identified the oxidized reaction product for CCPO-catalyzed dehalogenation of 2,4,6-trihalophenols as the corresponding 2,6-dihalo-1,4-benzoquinones. This reaction has previously been reported for two His-ligated heme-containing peroxidases (see Osborne, R. L.; Taylor, L. O.; Han, K. P.; Ely, B.; Dawson, J. H. Biochem. Biophys. Res. Commun. 2004, 324, 1194-1198), but this is the first example of a Cys-ligated heme-containing peroxidase functioning as a dehaloperoxidase. The relative catalytic efficiency (turnover number) of CCPO reported herein is comparable to that of horseradish peroxidase (Ferrari, R. P.; Laurenti, E.; Trotta, F. J. Biol. Inorg. Chem. 1965, 4, 232-237). The mechanism of dehalogenation has been probed using p-halophenols as substrates. Here the major product is a dimer with 1,4-benzoquinone as the minor product. An electron-transfer mechanism is proposed that accounts for the products formed from both the 2,4,6-trihalo- and p-halophenols. Finally, we note that this is the first case of a peroxidase known primarily for its halogenation ability being shown to also dehalogenate substrates. 相似文献
Furfuryl glycidyl ether (FGE) represents a highly versatile monomer for the preparation of reversibly cross‐linkable nanostructured materials via Diels–Alder reactions. Here, the use of FGE for the mid‐chain functionalization of a P2VP‐b‐PEO diblock copolymer is reported. The material features one furan moiety at the block junction, P2VP68‐FGE‐b‐PEO390, which can be subsequently addressed in Diels–Alder reactions using maleimide‐functionalized counterparts. The presence of the FGE moiety enables the introduction of dyes as model labels or the formation of hetero‐grafted brushes as shell on hybrid Au@Polymer nanoparticles. This renders P2VP68‐FGE‐b‐PEO390, a powerful tool for selective functionalization reactions, including the modification of surfaces.
The unique properties of plasmonic nanostructures have fuelled research based on the tremendous amount of potential applications. Their tailor‐made assemblies in combination with the tunable size and morphology of the initial building blocks allow for the creation of materials with a desired optical response. In this respect, it is crucial to synthesize nanoparticles with a defined shape that are at the core of such developments. Moreover, the interaction of individual nanoparticles with an incident electromagnetic field cannot only be influenced by their structure, but in fact, also by their spatial arrangement to each other. To harvest such opportunities, a profound theoretical understanding of these interactions is required as well as concise strategies to create such ordered assemblies. A quantitative evaluation of their optical properties can only be conducted when discrete structures of high uniformity can be achieved. As a consequence, separation steps have to be applied in order to obtain materials of high purity and uniformity. This also allows for an easier structural characterization of the nanoparticles and their assembled superstructures. In this progress report, an overview about the current development in this field of research is provided. 相似文献
The energy input and frequency shift of geodesic acoustic modes (GAMs) due to turbulence in tokamak edge plasmas are investigated in numerical two-fluid turbulence studies. Surprisingly, the turbulent GAM dispersion relation is qualitatively equivalent to the linear GAM dispersion but can have drastically enhanced group velocities. In up-down asymmetric geometry the energy input due to turbulent transport may favor the excitation of GAMs with one particular sign of the radial phase velocity relative to the magnetic drifts and may lead to pulsed GAM activity. 相似文献
Water-based Zn(II) bisterpyridine systems were used as fluorometric sensors for the detection of the nerve gas G mimics DMMP, DCP and DCNP. Analyte concentrations in the range of 10(-7) to 10(-6) M are detectable in solution. The utilization of a test stripe additionally allows the detection of organophosphonates from the gas phase. 相似文献
Blue emitting dyes bearing a luciferin analogous chromophore were attached to a polystyrene backbone. For this purpose, 4-hydroxy-1,3-thiazoles were functionalized with a styrene unit and polymerized using the reversible addition–fragmentation chain transfer (RAFT) polymerization technique. Two different chain transfer agents were investigated and one monomer was studied in terms of its kinetic behavior. The polymerization kinetics are presented and discussed in detail, showing a controlled polymerization behavior, resulting in well-defined copolymers with polydispersity indices below 1.2. The obtained polymers were characterized by size exclusion chromatography (SEC), 1H NMR, MALDI-TOF MS and UV–vis absorption and fluorescence spectroscopy. In addition, the UV–vis absorption and emission behavior was investigated in thin films. 相似文献
In this paper, we develop the mass and energy jump conditions for a vapor–liquid boundary within a porous medium. The analysis is restricted to a single fluid component and leads to the appropriate jump conditions for an evaporation front. The condition of local thermal equilibrium is assumed to exist in the homogeneous liquid and vapor regions, but not in the boundary region where rapid changes in the saturation occur. 相似文献
The present article describes a facile one-pot synthesis of a new series of 4,4′-(1,4-phenylene)-dipyrimidines ( 6a–c and 10a, b ) by the reaction of terephthalaldehyde ( 1 ), 2-acetylthiophene, and/or nitriles with S-benzylthiouronium chloride 3a . And also, the di-pyrimidinones 13a-d were obtained by the reaction of different amidines 3a–d and ethyl cyanoacetate ( 11 ) with terephthalaldehyde ( 1 ) under solvent-free conditions in the existence of sodium hydroxide which is found to be a more efficient base for these reactions. The final products were characterized by spectral data and elemental analysis, IR, MS, 1 H, and 13 C NMR spectroscopy. 相似文献