Mechanochemical treatment offers great potential for environmentally sustainable processing of chitin within the context of biomass valorization. Using powder X-ray diffraction, we show that crystallinity can be reduced by 50% in 2 h in a controlled way using a ball mill. We correlate this crystallinity reduction with a decrease in interchain hydrogen bonding using infrared spectroscopy as a structural probe. Furthermore, our quantitative interpretation of the spectra reveal a decrease in glycosidic linkage content and retention of N-acetyl groups. The addition of a natural clay, kaolinite, in the ball mill leads to a significant increase in the solubility of the milled materials (up to 75.8% water-soluble products in 6 h, cf. 35.0% without kaolinite). The products of this process were characterized as oligomers of N-acetyl-d-glucosamine (chitin oligomers) with degrees of polymerization (DP) between 1 and 5 using a new quantitative matrix-assisted laser desorption-ionization (MALDI-ToF) mass spectrometric method. These data were complemented by a colorimetric assay of reducing ends and size-exclusion chromatography (SEC). N-Acetyl-d-glucosamine (the monomer) and N,N′-diacetylchitobiose (the dimer) were obtained in yields of 5.1 and 3.9 wt %, respectively, within 6 h, which is comparable with yields of glucose and cellobiose from cellulose ball milling.

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The presence of sulfuroxyion compounds (thiosalts) in mining wastewater is a concern because of their potential for acidification of receiving water bodies. Despite extensive research, generation and kinetic information of thiosalt species under different pH and temperature conditions is not fully understood, especially under the range of conditions likely to be encountered in receiving ponds. As a result, it is difficult to design ponds or develop treatment technologies to treat these compounds. The authors present a summary of relevant information in terms of generation and kinetics of thiosalts, analytical methods for measuring their concentrations, and treatment of thiosalt wastes.

A molecularly imprinted polymer (MIP) film using catechol as the template was designed for adsorption of a range of phenols from water. Four different isotherm models (Langmuir (LI), Freundlich (FI), Langmuir–Freundlich (L-FI), and Brunauer, Emmett, and Teller (BET)) were used to study the MIP adsorption of five phenolic compounds: phenol (Ph), 2-methylphenol (2-MP), 3-methylphenol (3-MP), 2-chlorophenol (2-CP), and 4-teroctylphenol (4-OP). Each model was evaluated for its fit with the experimental data, and key parameters, including a number of binding sites and binding site energies, were compared. Though the LI, L-FI, and BET models showed good agreement for estimation of the number of binding sites and affinity for most adsorbates, no single model was suitable for all. The LI and L-FI models gave the best fitting statistics for the Ph, 2-MP, 3-MP, and 2-CP. The recognition of 4-OP, which has much higher binding affinities than the smaller phenolic compounds not attributable to hydrophobicity alone, was explained only by the BET model, which indicates the formation of multilayers. The BET model failed only with phenol. MIPs also showed higher adsorption capacities and improved homogeneity over the analogous non-imprinted polymers.

Amine-bis(phenolato)chromium(III) chloride complexes, [LCrCl], are capable of catalyzing the copolymerization of cyclohexene oxide with carbon dioxide to give poly(cyclohexane) carbonate. When combined with 4-(N,N-dimethylamino)pyridine (DMAP) these catalyst systems yield low molecular weight polymers with moderately narrow polydispersities. The coordination chemistry of DMAP with five amine-bis(phenolato)chromium(III) chloride complexes was studied by matrix assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS). The amine-bis(phenolato) ligands were varied in the nature of their neutral pendant donor-group and include oxygen-containing tetrahydrofurfuryl and methoxyethyl moieties, or nitrogen-containing N,N-dimethylaminoethyl or 2-pyridyl moieties. The relative abundance of mono and bis(DMAP) adducts, as well as DMAP-free ions is compared under various DMAP : Cr complex ratios. The [LCr](+) cations show the ability to bind two DMAP molecules to form six-coordinate complex ions in all cases, except when the pendant group is N,N-dimethylaminoethyl (compound ). Even in the presence of a 4 : 1 ratio of DMAP to Cr, no ions corresponding to [L3Cr(DMAP)2](+) were observed for the complex containing the tertiary sp(3)-hybridized amino donor in the pendant arm. The difference in DMAP-binding ability of these compounds results in differences in catalytic activity for alternating copolymerization of CO2 and cyclohexene oxide. Kinetic investigations by infrared spectroscopy of compounds 2 and 3 show that polycarbonate formation by 3 is twice as fast as that of compound 2 and that no initiation time is observed.