This article examines the photoxidation of a dye (rhodamine‐B, RhB) by visible‐light irradiation in the presence of a polyoxometalate (12‐tungstosilicic acid, H4SiW12O40), and compares it with the analogous process in the presence of TiO2. The photoreaction processes were examined by UV‐visible spectroscopy, fluorescence spectroscopy, high‐performance liquid chromatography (HPLC), liquid chromatography/mass spectral techniques (LC‐MS), and total organic carbon (TOC) assays in order to identify the intermediates produced. Formation of oxygen species, such as H2O2 and O2.−, was also investigated to clarify the details of the reaction pathway. With the use of SiW12O404− ions as the photocatalyst, the photoreaction leads mainly to N‐dealkylation of the chromophore skeleton. In contrast, cleavage of the whole conjugated chromophore structure predominates in the presence of TiO2. Strong O2.−/HO2.− ESR signals were detected in the TiO2 dispersions, whereas only weak ESR signals for the O2.− radical ion were seen in the SiW12O404− solutions during the irradiation period. Experimental results imply that reduction of O2 occurs by different pathways in the two photocatalytic systems.

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A new kind of biobased material named lignin-containing polyhydroxyurethane (LPHU) is prepared from bis­(6-membered cyclic carbonate) (BCC), dimer fatty diamine, and lignin for the first time. The preparation strategy is isocyanate-free, solvent-free, and catalyst-free, representing a green and environmentally friendly method to access polyurethane (PU)/lignin composites. The resultant LPHUs possess dual networks: a dynamic covalent network and a hydrogen bonding network, exhibiting superior mechanical strength, high thermal stability, excellent reprocessability/recyclability, and smart properties such as shape memory and self-healing. Potential application investigations indicate that the resultant LPHUs can be not only used for smart packaging label fabrication for heat-sensitive commodities but also further combined with natural cellulose paper to prepare paper-based electromagnetic shielding materials with high mechanical performance.

Organocatalysis is an important branch of catalysis for various organic transformations and materials preparation. Polymerizations promoted by organic catalysts can produce polymeric materials without any metallic residues, providing charming materials for high-value and sensitive domains such as biomedical applications, microelectronic devices and food packaging. Herein, we describe a fluorinated alcohol based catalytic system for polypeptide synthesis via catalytic ring-opening polymerization (ROP) of α -amino acid N -carboxyanhydride (NCA), fulfilling cocatalyst free, metal free, high rate and high selectivity. During polymerization, the fluorinated alcohol catalyst forms multiple dynamic hydrogen bonds with the initiator, monomer and propagating polymer chain. These cooperative hydrogen bonding interactions activate the NCA monomers and simultaneously protect the overactive initiator/propagating polymer chain-ends, which offers the whole polymerization with high activity and selectivity. Mechanistic studies indicate a monocomponent-multifunctional catalytic mode of fluorinated alcohol. This finding provides a metal free and fast approach to access well-defined polypeptides.

Four model polyurethane (PU) hard segments were synthesized by reaction of butanol with four typical diisocyanates. The four diisocyanates were aromatic 4,4′-diphenylmethane diisocyanate (4,4′-MDI) and MDI-50 (50% mixture of 2,4′-MDI and 4,4′-MDI), cycloaliphatic 4,4′-dicyclohexylmethane diisocyanate (HMDI) and linear aliphatic 1,6-hexamethylene diisocyanate (HDI). FTIR, 1H NMR, 13C NMR, MS, X-ray and DSC methods were employed to determine their structures and to analyse their crystallization behaviours and hydrogen bonding interactions. Each of the four PU compounds prepared in the present work displays unique spectral characteristics. The FTIR bands and NMR resonance peaks assigned in the four samples thus provide a reliable database and starting point for investigating the relationship between hard segment structure and the crystallization and hydrogen bonding behaviour in more complex-segmented PU compositions.

Vitrimer, the third category of polymer materials, combines the properties of traditional thermosets and thermoplastics and has gained much interest from industry since the first report in 2011. Currently, many researchers focus on the exploration of new chemistry for novel vitrimer synthesis but pay less attention to the fabrication of vitrimer composites based on known vitrimer systems. The latter can not only largely decrease the cost of vitrimers but also provide a facile way to increase the variety of vitrimer-based materials and extend the applications of vitrimers in different fields. In this study, we developed a new class of vitrimer composite using polycarbonate as a matrix and natural cellulose paper as the reinforcing framework for the first time. The resultant materials possess exceptional mechanical properties and great thermal/chemical stability, simultaneously exhibiting a series of smart properties, such as shape-memory, reshaping, self-healing, and reprocessing. Noteworthily, the two main components of the resultant materials, polycarbonate and natural cellulose, can be easily recycled under mild conditions; thus, these new vitrimer composites qualify as novel green and sustainable materials.

By associating primary (slow but controlled ring-opening polymerization; ROP) and tertiary (fast but uncontrolled ROP) amines in the same molecule, a novel highly active organocatalytic system proceeding by an accelerated amine mechanism through monomer activation (AAMMA) and leading to living ROP of α-amino acid N-carboxyanhydrides at room temperature was successfully developed.

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