Elucidation of the chemical structure and formation mechanism of humins is a requisite to further improve the efficiency of acid‐catalyzed biomass conversion. Through a low‐temperature approach, the key intermediates resulting in the formation of 5‐hydroxymethylfurfural (HMF)‐derived humins were captured, revealing multiple elementary reactions such as etherification, esterification, aldol condensation, and acetalization. Through humin characterization, it was found out that the aldol condensation moiety between aldehyde group and levulinic acid is critical to justify the characteristic IR peaks (1620 and 1710 cm−1) and aromatic fragments from pyrolysis GC–MS. Based on the investigations by means of HPLC–MS/MS, IR, pyrolysis GC–MS, and SEM, the structural models of humins at different temperatures were proposed, which are comprised of the elementary reaction types confirmed by the key intermediates. Humin structures with varying content of aldol condensation could be controllably synthesized under different reaction conditions (temperature and time), demonstrating the evolution process of HMF‐derived humins.
Surface and interface properties are important in controlling the yield and efficiency of the photochemically initiated immobilization. Using a silane-functionalized perfluorophenyl azide (PFPA-silane) as the photoactive cross-linker, the immobilization of polymers was studied by adjusting the density of the surface azido groups. Dilution of the photolinker resulted in a gradual decrease in the density of surface azido groups as well as the thickness of the immobilized film. When a nonphotoactive silane was added to PFPA-silane, the film thickness decreased more rapidly, suggesting that the additive competed with PFPA-silane and effectively reduced the density of the surface azido groups. The effect of surface topography was studied by adding a nonphotoactive silane with either a shorter (n-propyltrimethoxysilane (PTMS)) or a longer spacer (n-octadecyltrimethoxysilane (ODTMS)). In most cases the long chain ODTMS shielded the surface azido groups, resulting in a more rapid decrease in film thickness as compared to PTMS treated under the same conditions. As the density of the surface azido groups decreased, the immobilized polymer changed from smooth films to patched structures and, eventually, single polymer molecules.
The host-guest chemistry between a series of 1-alkyl-3-methyl-imidazolium bromide ([C(n)mim]Br) guests and the macrocyclic host molecule cucurbit[6]uril (CB[6]) in an aqueous system is systematically studied in neutral aqueous media. Both 1D and 2D NMR experiments in conjunction with isothermal titration calorimetry (ITC) unveil the binding characteristics of the host-guest interaction. Solution binding constants (K(a)) up to 10(5) M(-1) are measured directly. Additionally, this [C(n)mim]Br-CB[6] interaction was found to significantly increase the solubility of CB[6] in neutral water, in some cases by at least four orders of magnitude. From these studies, a detailed host-guest binding model has been constructed and is fully discussed. In this model, the delocalized positive charge on the imidazolium ring becomes partially localized on either one of the nitrogen atoms upon complexation with CB[6]. Localization of the positive charge is directly related to the length of the "1-alkyl" chain on the imidazolium ring, which causes an induced local dipole subsequently allowing for an ion-dipole interaction with the carbonyl portal of CB[6].
Cucurbit[6]uril was dissolved through encapsulation of an imidazolium-based ionic liquid guest in a pure water environment and the dissolution ability could be tuned by augmenting the imidazolium structure.
Selective and green conversion of chitin to levulinic acid has been realized by catalysis of ionic liquids up to a yield of 67.0%. Two-approach mechanism was proposed in the presence of H-bonding networks mainly contributed by the N-acetyl groups.
Stuck fast: The covalent immobilization of polymeric single molecules is achieved by the photochemically induced CH/NH insertion reaction of perfluorophenylazides (see picture). When the concentration of the surface azido groups is decreased, isolated polymeric single molecules are observed. This technique is especially suited for materials that do not possess functional groups and are difficult to be immobilized by other means.
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