Nickel-Catalyzed Ethylene Dimerization Based on PNP(NR2)2 Ligands

Nickel (II) complexes stabilized by PNP(NR2)2 (L1: R = Methyl, L2: R = ethyl, L3: R = isopropyl) ligands were synthesized and characterized. A narrow range of products was observed for catalytic systems containing nickel complexes and ethyl aluminum dichloride (EADC). All exhibit considerable activity in the ethylene dimerization to produce 1-butene. Precatalyst 1 is the most conducive for ethylene dimerization, producing 83.4% C4 (1-C4 36.8%) and 103.0 × 105 g/(molNi·h) in terms of its activity under the appropriate conditions. By adjusting the conditions of the catalytic system for precatalyst 2, high C4 selectivity (88.1%) with reasonable activity (76.9 × 105 g/(molNi·h)) can be obtained. The X-ray single-crystal analysis of complexes presents mononuclear bidentate coordination at the Ni center, and the relationship between certain bite angles may also imply catalytic performance

Nickel-Catalyzed Ethylene Dimerization Based on PNP(NR₂)₂ Ligands

Nickel (II) complexes stabilized by PNP(NR2)2 (L1: R = Methyl, L2: R = ethyl, L3: R = isopropyl) ligands were synthesized and characterized. A narrow range of products was observed for catalytic systems containing nickel complexes and ethyl aluminum dichloride (EADC). All exhibit considerable activity in the ethylene dimerization to produce 1-butene. Precatalyst 1 is the most conducive for ethylene dimerization, producing 83.4% C4 (1-C4 36.8%) and 103.0 × 105 g/(molNi·h) in terms of its activity under the appropriate conditions. By adjusting the conditions of the catalytic system for precatalyst 2, high C4 selectivity (88.1%) with reasonable activity (76.9 × 105 g/(molNi·h)) can be obtained. The X-ray single-crystal analysis of complexes presents mononuclear bidentate coordination at the Ni center, and the relationship between certain bite angles may also imply catalytic performance

Chromium Catalysts Based on Unsymmetrical PNP Ligands for Selective Ethylene Tri-/Tetramerization: Effect of Electron-Withdrawing/Donating Substituents on Catalytic Performance

The in situ formation and activation of Cr(III) catalysts based on unsymmetrical PNP ligands yield efficient catalytic systems for selective ethylene tri-/tetramerization. The electronic nature (electron-withdrawing or electron-donating) and position (para or meta) of the substituents over the phenyl rings of the PNP, the nature of cocatalyst (DMAO/AlEt3 and MMAO-3A), and reaction conditions have been observed to have a marked impact on catalytic performance, particularly catalytic activity. Ligand L2, bearing 4-(trifluoromethyl)phenyl substituents, yielded 33.6 kg(product).g(Cr)−1·h−1 catalytic activity with 57.7% C8 selectivity under optimal conditions. Ligand L4, having para-tolyl substituents, yielded 43.3 kg(product).g(Cr)−1·h−1 with 59.0% C8 selectivity under optimum conditions. Changing the positions of both the electron-withdrawing and electron-donating substituents from para to meta over the phenyls of the PNP may lead to both catalytic systems exhibiting poor performance

Fabrication and properties of strip casting 4.5 wt% Si steel thin sheet

Three 4.5 wt% Si steel thin sheets with different thicknesses were efficiently fabricated by twin-roll strip casting, warm rolling and cold rolling followed by final annealing. A comprehensive investigation from the workability of the as-cast strip to the magnetic property of the produces was performed to illustrate the superiority of the new materials. The results show that the as-cast strip, which has a much lower Vickers hardness than that of the 6.5 wt% Si steel, is suitable for rolling processing. The X-ray diffraction (XRD) and transmission electron microscopy (TEM) studies confirm that no ordering phase exists in the as-cast strip. The cold-rolled thin sheets exhibit good surface quality without edge cracks. Furthermore, all the three 4.5 wt% Si steel thin sheets possess relative strong //ND texture and present high magnetic inductions and low iron losses after finial annealing

Upconversion Effective Enhancement by Producing Various Coordination Surroundings of Rare-Earth Ions

In this manuscript, we present a simple route to enhance upconversion (UC) emission by producing two different coordination sites of trivalent cations in a matrix material and adjusting crystal field asymmetry by Hf⁴⁺ co-doping. A cubic phase, Y_3.2Al_0.32Yb_0.4Er_0.08F₁₂, with these structural characteristics was synthesized successfully by introducing a small ion (Al³⁺) into YF₃. X-ray diffraction (XRD), nuclear magnetic resonance (NMR), transmission electron microscopy (TEM), X-ray spectroscopy (XPS), and fluorescence spectrophotometry (FS) were employed for its crystalline structure and luminescent property analysis. As a result, the coordination environments of the rare-earth ions were varied more obviously than a hexagonal NaYF₄ matrix with the same Hf⁴⁺ co-doping concentration, with vertical comparison, UC luminescent intensities of cubic Y_3.2Al_0.32Yb_0.4Er_0.08F₁₂ were largely enhanced (∼32–80 times greater than that of different band emissions), while the maximum enhancement of hexagonal NaYF₄ was by a factor of ∼12. According to our experimental results, the mechanism has been demonstrated involving the crystalline structure, crystal field asymmetry, luminescence lifetime, hypersensitive transition, and so on. The study may be helpful for the design and fabrication of high-performance UC materials

Upconversion Effective Enhancement by Producing Various Coordination Surroundings of Rare-Earth Ions

In this manuscript, we present a simple route to enhance upconversion (UC) emission by producing two different coordination sites of trivalent cations in a matrix material and adjusting crystal field asymmetry by Hf⁴⁺ co-doping. A cubic phase, Y_3.2Al_0.32Yb_0.4Er_0.08F₁₂, with these structural characteristics was synthesized successfully by introducing a small ion (Al³⁺) into YF₃. X-ray diffraction (XRD), nuclear magnetic resonance (NMR), transmission electron microscopy (TEM), X-ray spectroscopy (XPS), and fluorescence spectrophotometry (FS) were employed for its crystalline structure and luminescent property analysis. As a result, the coordination environments of the rare-earth ions were varied more obviously than a hexagonal NaYF₄ matrix with the same Hf⁴⁺ co-doping concentration, with vertical comparison, UC luminescent intensities of cubic Y_3.2Al_0.32Yb_0.4Er_0.08F₁₂ were largely enhanced (∼32–80 times greater than that of different band emissions), while the maximum enhancement of hexagonal NaYF₄ was by a factor of ∼12. According to our experimental results, the mechanism has been demonstrated involving the crystalline structure, crystal field asymmetry, luminescence lifetime, hypersensitive transition, and so on. The study may be helpful for the design and fabrication of high-performance UC materials

EVLncRNAs: a manually curated database for long non-coding RNAs validated by low-throughput experiments

Long non-coding RNAs (lncRNAs) play important functional roles in various biological processes. Early databases were utilized to deposit all lncRNA candidates produced by high-throughput experimental and/or computational techniques to facilitate classification, assessment and validation. As more lncRNAs are validated by low-throughput experiments, several databases were established for experimentally validated lncRNAs. However, these databases are small in scale (with a few hundreds of lncRNAs only) and specific in their focuses (plants, diseases or interactions). Thus, it is highly desirable to have a comprehensive dataset for experimentally validated lncRNAs as a central repository for all of their structures, functions and phenotypes. Here, we established EVLncRNAs by curating lncRNAs validated by low-throughput experiments (up to 1 May 2016) and integrating specific databases (lncRNAdb, LncRANDisease, Lnc2Cancer and PLNIncRBase) with additional functional and disease-specific information not covered previously. The current version of EVLncRNAs contains 1543 lncRNAs from 77 species that is 2.9 times larger than the current largest database for experimentally validated lncRNAs. Seventy-four percent lncRNA entries are partially or completely new, comparing to all existing experimentally validated databases. The established database allows users to browse, search and download as well as to submit experimentally validated lncRNAs. The database is available at here