Nickel/Photoredox-Catalyzed Carbonylative Cross-Electrophile Coupling of Organohalides and Carboxylic Acid Esters with Phenyl Formate.

A photoinduced nickel-catalyzed reductive carbonylative coupling from organohalides and N-(acyloxy)phthalimide esters with phenyl formate as the carbonyl source has been developed. This reaction could perform smoothly under mild conditions, and a series of aryl-alkyl and alkyl-alkyl unsymmetrical ketones were produced without the need of stoichiometric metal reductants. Mechanistic studies indicate that this reaction was initiated from radical capture by Ni(I)-carbonyl species and subsequent rapid carbonyl insertion.

Construction of Macromolecules of Depolymerized Lignite.

Preparing ash-less coal and further converting it into chemicals is an efficient and promising means for lignite utilization. This work performed depolymerization of lignite to prepare ash-less coal (SDP) and separated it into the hexane-soluble fraction (HS), toluene-soluble fraction (TS), and tetrahydrofuran-soluble fraction (THFS). The structure of SDP and those of subfractions were characterized by elemental analysis, gel permeation chromatography, Fourier transform infrared spectroscopy, and synchronous fluorescence spectroscopy. The results show that SDP is a mixture of aromatic derivatives containing alkyl substituents and oxygen-containing functional groups. The number of condensed aromatic rings, the amount of oxygen-containing functional groups, and the molecular weight gradually increase as HS < TS < THFS. SDP was further analyzed by 1H-NMR and 13C-NMR to calculate its structural parameters. The macromolecule of THFS contains 15.8 total ring systems with 9.2 aromatic rings and 6.6 naphthenic rings. On average, each THFS molecule contains 6.1 alcohol hydroxyl groups, 3.9 phenol hydroxyl groups, 1.4 carboxyl groups, and 1.0 inactive oxygen-containing functional groups. The dominant reactions occurred during depolymerization are the breakage of ether linkages. The average THFS molecule consists of 3.3 structural units with aromatic nuclei (2.8 rings on average) linked with methylene, naphthene, and so forth.

Highly Conjugated Two-dimensional Covalent Organic Frameworks for Efficient Iodine Uptake.

Radioactive iodine in nuclear waste would be harmful to nature and human health. The design of adsorbents for iodine capture with high efficiency still remains a challenge. Herein, two highly conjugated two-dimensional covalent organic frameworks (TFPB-BPTA-COF and TFPB-PyTTA-COF) have been successfully constructed. Both COFs possess high porosity, stability, and a high π-conjugated framework. Impressively, TFPB-PyTTA-COF exhibits an excellent iodine uptake value of up to 5.6 g g-1 , which is superior to most reported COF-based adsorbents for iodine capture.

[Fluorescence spectroscopy characterization of asphaltene liquefied from coal and study of its association structure].

Structure and association of asphaltenes from coal direct hydroliquefaction were studied by fluorescence spectrometry and UV-Vis absorption spectrometry in this paper. The results indicate that asphaltene is aromatic mixtures mainly containing naphthalene nucleus and shows strong fluorescent characteristic. The forming of exciplex between asphaltene and solvent results in the red shift of fluorescence peak and fluorescence quenching of asphaltene that increases with the polarity and electron acceptability. The self-aggregation of asphaltene is formed by non-covalent bond interaction, so that the asphaltene liquefied at higher temperture that shows high aromaticity has stronger association than that liquefied at lower temperature. Aggregation of asphaltene has been found to be a gradual process, in which there is no critical aggregation constant observed, and the inflection point of the plot of apparent fluorescence intensity as a function of asphaltene concentration varies with the excitation wavelength.