Electrooxidation Is a Promising Approach to Functionalization of Pyrazole-Type Compounds

The review summarizes for the first time the poorly studied electrooxidative functionalization of pyrazole derivatives leading to the C–Cl, C–Br, C–I, C–S and N–N coupling products with applied properties. The introduction discusses some aspects of aromatic hydrogen substitution. Further, we mainly consider our works on effective synthesis of the corresponding halogeno, thiocyanato and azo compounds using cheap, affordable and environmentally promising electric currents.

High Jc and low anisotropy of hydrogen doped NdFeAsO superconducting thin film

The recent realisations of hydrogen doped LnFeAsO (Ln = Nd and Sm) superconducting epitaxial thin films call for further investigation of their structural and electrical transport properties. Here, we report on the microstructure of a NdFeAs(O,H) epitaxial thin film and its temperature, field, and orientation dependencies of the resistivity and the critical current density Jc. The superconducting transition temperature Tc is comparable to NdFeAs(O,F). Transmission electron microscopy investigation supported that hydrogen is homogenously substituted for oxygen. A high self-field Jc of over 10 MA/cm2 was recorded at 5 K, which is likely to be caused by a short London penetration depth. The anisotropic Ginzburg–Landau scaling for the angle dependence of Jc yielded temperature-dependent scaling parameters γJ that decreased from 1.6 at 30 K to 1.3 at 5 K. This is opposite to the behaviour of NdFeAs(O,F). Additionally, γJ of NdFeAs(O,H) is smaller than that of NdFeAs(O,F). Our results indicate that heavily electron doping by means of hydrogen substitution for oxygen in LnFeAsO is highly beneficial for achieving high Jc with low anisotropy without compromising Tc, which is favourable for high-field magnet applications.

Direct C-H Alkoxylation of BODIPY Dyes via Cation Radical Accelerated Oxidative Nucleophilic Hydrogen Substitution: A New Route to Building Blocks for Functionalized BODIPYs

Oxidative nucleophilic -hydrogen substitution (ONHS) is a direct method for BODIPY functionalization. However, it was hampered by low reactivity of BODIPYs toward weak nucleophiles. Herein, we develop a cation radical...

Benchmark ab initio stationary-point characterization of the complex potential energy surface of the multi-channel Cl + CH3NH2 reaction

We characterize the exothermic low/submerged-barrier hydrogen-abstraction (HCl + CH2NH2/CH3NH) as well as, for the first time, the endothermic high-barrier amino-substitution (CH3Cl + NH2), methyl-substitution (NH2Cl + CH3), and hydrogen-substitution (CH2ClNH2/CH3NHCl...

Assessment of Hydrogen and Natural Gas Mixtures in a Large Bore Gas Engine for Power Generation

Now more than ever there is a growing global interest to reduce greenhouse gas (GHG) emissions originating from internal combustion engines. One approach consists in the use of hydrogen instead of fossil fuels. Large bore gas engines for power generation are often fueled by gases with high methane content. Relative to natural gas-fueled engines, the power densities of premixed or port-fuel-injected hydrogen engines are limited due to low volumetric efficiencies and moreover by occurring irregular combustion events (knocking, backfire). The paper presents results from experimental investigations of the impact of different hydrogen substitution rates in natural gas on performance, emissions and operating limits on a single cylinder research engine. The engine is representative for a large bore gas engine for power generation and operates using an open chamber combustion concept with lean mixtures. Essentially, THC, CO2 and CO emissions decrease with rising hydrogen content of the fuel gas. Even with low concentrations of hydrogen in the fuel gas, significant reductions in THC emissions could be demonstrated. Usually NOX emissions will rise with unchanged operating parameters. However, if excess-air ratio and spark timing are adjusted, a net reduction of NOX emissions can be achieved while the impact on brake thermal efficiency is small. Furthermore, the paper outlines potential mitigation strategies to expand the operational limits with respect to power density with high hydrogen substitution rates.

Benchmark ab initio characterization of the abstraction and substitution pathways of the OH + CH4/C2H6 reactions

We report benchmark ab initio stationary-point properties for the hydrogen-abstraction, hydrogen-substitution, and methyl-substitution pathways of the OH + CH4/C2H6 reactions.

Direct sulfonylation of BODIPY dyes with sodium sulfinates through oxidative radical hydrogen substitution at the α-position

A series of α-sulfonated BODIPYs were efficiently synthesized from sodium sulfinates via a radical process, and were demonstrated as new fluorescent probes for selective biothiol detection.