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排序方式: 共有143条查询结果,搜索用时 15 毫秒
61.
Gina L. Morgan Prof. Bo Li 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(48):21571-21575
The Pseudomonas virulence factor (pvf) operon is essential for the biosynthesis of two very different natural product scaffolds: the (dihydro)pyrazine-N-oxides and the diazeniumdiolate, valdiazen. PvfB is a member of the non-heme diiron N-oxygenase enzyme family that commonly convert anilines to their nitroaromatic counterparts. In contrast, we show that PvfB catalyzes N-oxygenation of the α-amine of valine, first to the hydroxylamine and then the nitroso, while linked to the carrier protein of PvfC. PvfB modification of PvfC-tethered valine was observed directly by protein NMR spectroscopy, establishing the intermediacy of the hydroxylamine. This work reveals a central role for PvfB in the biosynthesis of (dihydro)pyrazine-N-oxides and valdiazen. 相似文献
62.
Tim Fiedler Stephanie Dirksmeyer Dr. Markus Seibald Dr. Franziska Hummel Dr. Simon Peschke Dr. Gina M. Achrainer Dr. Daniel Bichler 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(4):795-798
Innovative materials for phosphor-converted white light-emitting diodes (pc-LEDs) are much sought after due to the huge potential of the LED technology to reduce energy consumption worldwide. One of the main levers for further improvements are the conversion phosphors. The system Ca1−xSrxAlSiN3:Eu2+ currently provides one of the most important red-emitting phosphors for pc-LEDs. We report the discovery of the new polymorph β-Ca1−xSrxAlSiN3:Eu2+ which allows for significant improvements to LED efficacies. It crystallizes in the orthorhombic space group Pbcn with lattice parameters a=982.43(10) pm, b=575.2(1) pm and c=516.12(5) pm. Compared to α-Ca1−xSrxAlSiN3:Eu2+, its emission shows a significantly reduced spectral full-width at half maximum (FWHM). With that, we demonstrated 3 % efficacy increase for white light-emitting pc-LEDs. The new polymorph can easily be industrialised, because the synthesis works on the same equipment as α-Ca1−xSrxAlSiN3:Eu2+. 相似文献
63.
An erbium-doped transparent glass ceramic, consisting of LaF3 nanocrystallites with a characteristic length of approximately 20 nm embedded in an aluminosilicate glass matrix and exhibiting infrared-to-green up-conversion, has been studied. The degree of erbium partitioning into the nanocrystallite phase was found using energy transfer coefficients determined from bulk Er3+:LaF3 samples. This transparent glass ceramic sample was found to have a partitioning fraction of 19 +/- 5%. 相似文献
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65.
Alkyldimesitylboranes, yield anions1, Mes2BHR, that on reaction with oxiranes followed by oxidation give 1,3-diols. These anions are thus the operational equivalent of RHOH. The scope and limitations of the new process are delineated. 相似文献
66.
Gina Kaysan Nicolas Schork Sabrina Herberger Gisela Guthausen Matthias Kind 《Magnetic resonance in chemistry : MRC》2022,60(7):615-627
Increasing the efficiency of disperse phase crystallization is of great interest for melt emulsion production as the fraction of solidified droplets determines product quality and stability. Nucleation events must appear within every single one of the μm-sized droplets for solidification. Therefore, primary crystallization requires high subcooling and is, thus, time and energy consuming. Contact-mediated nucleation is a mechanism for intensifying the crystallization process. It is defined as the successful nucleation of a subcooled liquid droplet induced by contact with an already crystallized droplet. We investigated contact-mediated nucleation under shear flow conditions up to shear rates of 457 s−1 for a quantitative assessment of this mechanism. Rheo-nuclear magnetic resonance was successfully used for the time-resolved determination of the solids fraction of the dispersed phase of melt emulsions upon contact-mediated nucleation events. The measurements were carried out in a dedicated Taylor–Couette cell. The efficiency of contact-mediated nucleation decreased with increasing shear rate, whereas the effective second order kinetic constant increased approximately linearly at small shear rates and showed a linear decrease for shear rates higher than about 200 s−1. These findings are in accordance with coalescence theory. Thus, the nucleation rate is optimal at specific flow conditions. There are limitations for successful inoculation at a low shear rate because of rare contact events and at a high shear rate due to too short contact time. 相似文献
67.
Zaicheng Sun Dong Ha Kim Markus Wolkenhauer Gabriela Gina Bumbu Wolfgang Knoll Jochen S Gutmann 《Chemphyschem》2006,7(2):370-378
High-density arrays of titania nanoparticles were prepared using a polystyrene-b-poly(ethylene oxide) block copolymer (PS-b-PEO) as a template and a titanium tetraisopropoxide based sol-gel precursor as titania source via a spin-coating method. The hydrophilic titania sol-gel precursor was selectively incorporated into hydrophilic PEO domains of PS-b-PEO and form titania nanoparticle arrays, due to a microphase separation between the PS block and the sol-gel/PEO phase. Field emission scanning electron microscopy (FESEM) and scanning probe microscopy (SPM) images showed that the uniformity and long-range order of the titania/PEO domains improved with increasing sol-gel precursor amount. Grazing incidence small-angle X-ray scattering (GISAXS) results indicate that the ordered structures exist over large length scales. Titania nanocrystal arrays of anatase modification were obtained by calcination at 600 degrees C for 4 h. After calcination, separated particles were observed for low and medium amounts of sol-gel precursors. Films with higher precursor amounts showed wormlike structures due to the aggregation between neighboring particles. Removal of the polymer matrix via UV treatment leads to highly ordered arrays of amorphous titania while retaining the domain size and interparticle distance initially present in the hybrid films. Photoluminescence (PL) properties were investigated for samples before and after calcination. The PL intensity increases with the increasing amount of sol-gel precursor. Bands at 412 nm were ascribed to self-trapped exitons and bands at 461 and 502 nm to oxygen vacancies, respectively. Uncalcined or UV-treated samples also showed PL properties similar to calcined samples, indicating that the local environment of the titanium atoms is similar to the environment of the crystalline anatase modification. 相似文献
68.
Peter J. A. In't Veld Esther M. Velner Peter Van De Witte Jennie Hamhuis Pieter J. Dijkstra Jan Feijen 《Journal of polymer science. Part A, Polymer chemistry》1997,35(2):219-226
AB block copolymers of ϵ-caprolactone and (L )-lactide could be prepared by ring-opening polymerization in the melt at 110°C using stannous octoate as a catalyst and ethanol as an initiator provided ϵ-caprolactone was polymerized first. Ethanol initiated the polymerization of ϵ-caprolactone producing a polymer with ϵ-caprolactone derived hydroxyl end groups which after addition of L -lactide in the second step of the polymerization initiated the ring-opening copolymerization of L -lactide. The number-average molecular weights of the poly(ϵ-caprolactone) blocks varied from 1.5 to 5.2 × 103, while those of the poly(L -lactide) blocks ranged from 17.4 to 49.7 × 103. The polydispersities of the block copolymers varied from 1.16 to 1.27. The number-average molecular weights of the polymers were controlled by the monomer/hydroxyl group ratio, and were independent on the monomer/stannous octoate ratio within the range of experimental conditions studied. When L -lactide was polymerized first, followed by copolymerization of ϵ-caprolactone, random copolymers were obtained. The formation of random copolymers was attributed to the occurrence of transesterification reactions. These side reactions were caused by the ϵ-caprolactone derived hydroxyl end groups generated during the copolymerization of ϵ-caprolactone with pre-polymers of L -lactide. The polymerization proceeds through an ester alcoholysis reaction mechanism, in which the stannous octoate activated ester groups of the monomers react with hydroxyl groups. © 1997 John Wiley & Sons, Inc. 相似文献
69.
Chiarella GM Cotton FA Dalal NS Murillo CA Wang Z Young MD 《Inorganic chemistry》2012,51(9):5257-5263
Three rare compounds have been synthesized and structurally characterized; these species have paddlewheel structures and Re(2)(7+) cores surrounded by four bicyclic guanidinates and two axial ligands along the Re-Re axis. Each possesses a formal bond order of 3.5 and a σ(2)π(4)δ(1) electronic configuration that entails the presence of one unpaired electron for each compound. The guanidinate ligands characterized by having CH(2) entities and a central C(N)(3) unit that joins two cyclic units--one having two fused 6-membered rings (hpp) and the other having a 5- and a 6-membered ring fused together (tbn)--allowed the isolation of [Re(2)(tbn)(4)Cl(2)]PF(6), 1, [Re(2)(tbn)(4)Cl(2)]Cl, 2, and [Re(2)(hpp)(4)(O(3)SCF(3))(2)](O(3)SCF(3)), 3. Because of the larger bite angle of the tbn relative to the hpp ligand, the Re-Re bond distances in 1 and 2 (2.2691(14) and 2.2589(14) ?, respectively) are much longer than that in 3 (2.1804(8) ?). Importantly, electron paramagnetic resonance (EPR) studies at both X-band (~9.4 GHz) and W-band (112 GHz) in the solid and in frozen solution show unusually low g-values (~1.75) and the absence of zero-field splitting, providing direct evidence for the presence of one metal-based unpaired electron for both 1 and 3. These spectroscopic data suggest that the unsymmetrical 5-/6-membered ligand leads to the formation of isomers, as shown by significantly broader EPR signals for 1 than for 3, even though both compounds possess what appears to be similar ideal crystallographic axial symmetry on the X-ray time scale. 相似文献
70.