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.