A Methoxyamine-Protecting Group for Organic Radical Battery Materials-An Alternative Approach.

An alternative synthetic route towards the widely employed electroactive poly(TEMPO methacrylate) (PTMA) via a thermally robust methoxyamine-protecting group is demonstrated herein. Protection of the radical moiety of hydroxy-TEMPO with a methyl functionality and subsequent esterification with methacrylic anhydride allows the high-yielding formation of the novel monomer methyl-TEMPO methacrylate (MTMA). The polymerization of MTMA to poly(MTMA) (PMTMA) is investigated via free radical polymerization and reversible addition-fragmentation chain-transfer polymerization (RAFT), a reversible-deactivation radical polymerization technique. Cleavage of the temperature-stable methoxyamine functionality by oxidative treatment of PMTMA with meta-chloroperbenzoic acid (mCPBA) releases the electroactive PTMA. The redox activity of PTMA was confirmed by cyclic voltammetry in lithium-ion coin cells.

Closing the textile loop: Enzymatic fibre separation and recycling of wool/polyester fabric blends.

Textile waste presents a serious environmental problem with only a small fraction of products from the fashion industry collected and re-used or recycled. The problem is exacerbated in the case of post-consumer waste by the mixture of different natural and synthetic fibres in blended textiles. The separation of mixed fibre waste, where garments are often multicomponent, presents a major recycling problem as fibres must be separated to single components to enable effective recycling. This work investigates the selective digestion of wool fibres from wool/polyester blended fabrics using an enzymatic approach. Complete degradation of wool fibres was achieved by application of a keratinase in a two-step process with addition of reducing agent and undigested polyester fibres were recovered. Electron microscopy showed complete breakdown of the natural fibres in the fabric blends, while spectroscopic and mechanical analysis of the recovered synthetic fibres confirmed that the enzymatic treatment had no significant impact on the properties of the polyester compared to virgin samples. The polyester fibres are therefore suitable to be recycled to polyester yarn and re-used in the manufacture of new garments or other products. The nutrient rich keratin hydrolysate could be used in microbial growth media or incorporated into bio-fertilisers or animal feed, contributing to the development of the circular economy.

New Spin on Organic Radical Batteries-An Isoindoline Nitroxide-Based High-Voltage Cathode Material.

Organic electrode materials are a highly promising and environmentally benign class of battery materials with radical polymers being at the forefront of this research. Herein, we report the first example of the 1,1,3,3-tetramethylisoindolin-2-yloxyl class of nitroxides as an organic electrode material and the synthesis and application of a novel styrenic nitroxide polymer, poly(5-vinyl-1,1,3,3-tetramethylisoindolin-2-yloxyl) (PVTMIO). The polymer was synthesized from the precursor monomer, 2-methoxy-5-vinyl-1,1,3,3-tetramethylisoindoline, and subsequent oxidative deprotection yielded the electroactive radical species. Cyclic voltammetry revealed a high oxidation potential of 3.7 V versus Li, placing it among the top of the nitroxide class of electrode materials. The suitability of PVTMIO for utilization in a high-voltage organic radical battery was confirmed with a discharge capacity of 104.7 mAh g-1, high rate performance, and stability under cycling conditions (90% capacity retention after 100 cycles), making it one of the highest reported organic p-dopable cathode materials.

Synthesis of enantiopure reversed structured ether lipids of the 1-O-alkyl-sn-2,3-diacylglycerol type.

This report describes the synthesis of reversed structured 1-O-alkyl-2,3-diacyl-sn-glycerols (DAGEs) possessing a pure saturated even number fatty acid (C6:0-C16:0) at the sn-2 position along with a pure EPA or DHA located at the terminal sn-3 position of the glycerol backbone of chimyl, batyl and selachyl alcohols. These adducts were synthesized by a highly efficient two-step chemoenzymatic process involving an immobilized Candida antarctica lipase to introduce pure EPA and DHA activated as oxime esters exclusively to the sn-3 terminal position of enantiopure chimyl, batyl and selachyl alcohols in excellent yields. The saturated fatty acids were subsequently incorporated to the remaining sn-2 position of the resulting 3-monoacylglyceryl ethers (3-MAGEs) using EDAC coupling agent in the presence of DMAP in very high to excellent yields (85%-98%). No losses of enantiomeric composition were observed during these processes. The multiple utilities of the resulting focused library of reversed structured DAGEs are discussed including how such compounds may possibly be utilized within the pharmaceutical area.