Lignin is a heterogeneous aromatic biopolymer that accounts for nearly 30% of the organic carbon on Earth and is one of the few renewable sources of aromatic chemicals. As the most recalcitrant of the three components of lignocellulosic biomass (cellulose, hemicellulose and lignin), lignin has been treated as a waste product in the pulp and paper industry, where it is burned to supply energy and recover pulping chemicals in the operation of paper mills. Extraction of higher value from lignin is increasingly recognized as being crucial to the economic viability of integrated biorefineries. Depolymerization is an important starting point for many lignin valorization strategies, because it could generate valuable aromatic chemicals and/or provide a source of low-molecular-mass feedstocks suitable for downstream processing. Commercial precedents show that certain types of lignin (lignosulphonates) may be converted into vanillin and other marketable products, but new technologies are needed to enhance the lignin value chain. The complex, irregular structure of lignin complicates chemical conversion efforts, and known depolymerization methods typically afford ill-defined products in low yields (that is, less than 10-20wt%). Here we describe a method for the depolymerization of oxidized lignin under mild conditions in aqueous formic acid that results in more than 60wt% yield of low-molecular-mass aromatics. We present the discovery of this facile C-O cleavage method, its application to aspen lignin depolymerization, and mechanistic insights into the reaction. The broader implications of these results for lignin conversion and biomass refining are also considered.

An efficient organocatalytic method for chemoselective aerobic oxidation of secondary benzylic alcohols within lignin model compounds has been identified. Extension to selective oxidation in natural lignins has also been demonstrated. The optimal catalyst system consists of 4-acetamido-TEMPO (5 mol %; TEMPO = 2,2,6,6-tetramethylpiperidine-N-oxyl) in combination with HNO3 and HCl (10 mol % each). Preliminary studies highlight the prospect of combining this method with a subsequent oxidation step to achieve C-C bond cleavage.

Diverse lignin samples have been subjected to a catalytic aerobic oxidation process, followed by formic-acid-induced hydrolytic depolymerization. The yield of monomeric aromatic compounds varies depending on the lignin plant source and pretreatment method. The best results are obtained from poplar lignin isolated via a acidolysis pretreatment method, which gives 42 wt% yield of low-molecular-weight aromatics. Use of other pretreatment methods and/or use of maple and maize lignins afford yields of aromatics ranging from 3 to 31 wt%. These results establish useful references for the development of improved oxidation/depolymerization protocols.

Background Creatine (CR) and sodium bicarbonate (SB) alone improve anaerobic performance. However, the ergogenic effects of CR and SB co-ingestion on taekwondo anaerobic performance remains unknown. Methods Forty trained taekwondo athletes (21 ± 1 y.; 180.5 ± 7.3 cm; 72.7 ± 8.6 kg) were randomized to: (i) CR and SB (CR + SB; 20 g of CR+ 0.5 g·kg− 1·d− 1 of SB), (ii) CR, (iii) SB, (iv) placebo (PLA), or (v) control (CON) for 5 days. Before and after supplementation, participants completed 3 bouts of a Taekwondo Anaerobic Intermittent Kick Test (TAIKT) to determine changes in peak power (PP), mean power (MP), and fatigue index (FI). Blood lactate (BL) was measured before, immediately following, and 3 min post-TAIKT. Results PP and MP increased over time (P < 0.05) following CR + SB, CR, and SB ingestion, with no changes in the PLA or CON groups. There was a greater increase over time in MP following CR + SB (Absolute Δ: 1.15 ± 0.28 W∙kg67) compared to CR (Absolute Δ: 0.43 ± 0.33 W∙kg67; P < 0.001) and SB (Absolute Δ: 0.73 ± 0.24 W∙kg67; P = 0.03). There were no significant time and condition effect for FI (P > 0.05). BL increased following exercise across all groups; however, CR + SB and SB post-exercise BL was lower compared to CR, PLA, and CON (P < 0.05). Conclusion Short-term CR and SB alone enhance TAIKT performance in trained taekwondo athletes. Co-ingestion of CR and SB augments MP compared to CR and SB alone, with similar PP improvements.

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The catalyst system consisting of 3,3'-(3,4-bis(dichloro-methylene)cyclobut-1-ene-1,2-diyl)bis(1-methyl-1H-imidazolium) bis(tetrafluoroborate), Pd(OAc)(2) and NaOtBu in toluene proved to be very effective for a broad variety of Suzuki-Miyaura reactions at room temperature. It is also suited for the synthesis of sterically hindered compounds including 2,6-di-tert-butyl-2'-substituted biaryls at elevated temperatures.

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Treatment of perchlorobuta-1,3-diene with 4-(N,N-dimethylamino)pyridine resulted in the formation of 1,1¢,1¢¢,1¢¢¢-(2,3-dichlorobuta-1,3-diene-1,1,4,4-tetrayl)tetrakis[4-(dimethylamino)pyridinium] tetrachloride (structure confirmed by X-ray analysis), which was converted into persulfurated butatrienes ([3]cumulenes), pentakis(sulfanyl)-substituted buta-1,3-dienes, or tetrakis(sulfanyl)-substituted 2,3-dichlorobuta-1,3-dienes by reactions with thiolates or a sulfinate. The outcome of the reaction depends on the reaction conditions and the substitution pattern of the starting sulfur nucleophiles.