Hierarchical Dual-Mode Efficient Tunable Afterglow via J-Aggregates in Single-Phosphor-Doped Polymer.

The development of polymer-based persistent luminescence materials with color-tunable organic afterglow and multiple responses is highly desirable for the applications in anti-counterfeiting, flexible displays and data-storage. However, achieving efficient persistent luminescence from a single-phosphor system with multiple responses remains a challenging task. Herein, a hierarchical dual-mode emission system is developed by doping 9H-pyrido[3,4-b]indole (PI2) into an amorphous polyacrylamide matrix, which exhibits color-tunable afterglow due to excitation-, temperature- and humidity-dependence. Notably, the coexistence of isolated state and J-aggregate state of the guest molecule not only provides excitation-dependent afterglow color, but also leads to hierarchical temperature-dependent afterglow color resulting from different thermally activated delayed fluorescence (TADF) and ultralong organic phosphorescence (UOP) behaviors of the isolated and aggregated states. The complex responsiveness based on the hierarchical dual-mode emission can serve for security features through inkjet printing and ink-writing. These findings may provide further insight into the regulated persistent luminescence by isolated and aggregated phosphors in doped polymer systems and expand the scope of stimuli-responsive organic afterglow materials for broader applications.

Robust Vanillin-Derived Poly(thioether imidazoles) as Both a Latent Curing and Toughening Agent for One-Component Epoxy Resins.

One-component epoxy resins based on latent curing agents have garnered research attention owing to their outstanding storage stability and excellent processability, while their development considerably depends on the design and preparation of sustainable latent curing agents. Herein, taking structural advantage of lignin-derived vanillin, a biobased polymerizable aromatic imidazole monomer with α,ω-diene functionality was designed and prepared, which was applicable in subsequent thiol-ene polymerization, yielding a series of robust poly(thioether imidazoles) with excellent tunability of the structure and properties. The findings indicated that the precursors comprising poly(thioether imidazole) and commercially available epoxy resins could keep their fluidity at 25 °C for over 90 days and rapidly cured into resins under elevated temperature, demonstrating that the poly(thioether imidazole) can serve as both a latent curing and toughening agent for one-component epoxy resins because of homopolymerization initiated by imidazole groups and the introduction of an aliphatic chain in the as-prepared poly(thioether imidazole) matrix.

Reversible covalent chemistry of carbon dioxide unlocks the recalcitrance of cellulose for its enzymatic saccharification.

To overcoming the natural recalcitrance of cellulose for glucose production via enzymatic hydrolysis, a new strategy of destroying hydrogen bond donor to reconstruct cellulose's hydrogen bonding network was developed via a mild reversible reaction of cellulose with CO2 catalyzed by organic bases. The reaction dynamics of cellulose with CO2 in the presence of organic bases was studied by using in situ IR. Investigation also included how the organic bases in pretreatment media and pretreatment parameters including CO2 pressure, pretreatment temperature and time affected the physical-chemical structure of cellulose by Fourier Transform Infrared Spectroscopy (FT-IR), X-ray diffraction (XRD), scanning electron microscopy (SEM) and Atomic force microscopy (AFM) and subsequent enzymatic scarification of cellulose. The findings showed that dissolution activation efficiency significantly correlated to various parameters, that can be optimized to be the tetramethyl guanidine (TMG)/CO2/DMSO solvent system at 50 °C, 2 MPa of CO2 for 2 h, by which a complete transformation the cellulose crystalline structure from I to II, and 100% glucose yield were achieved. The recyclability and usability are also investigated.

Unique gelation and rheological properties of the cellulose/CO2-based reversible ionic liquid/DMSO solutions.

Gelation and rheological behaviors of cellulose/CO2-based reversible ionic liquid (RIL)/DMSO solutions were investigated. The exponents of specific viscosity ηsp versus concentration c were determined for wood pulp (WP) and microcrystalline cellulose (MCC) solutions. The complex viscosity acquired using oscillatory shear closely follows the steady shear viscosity, thus revealing the applicability of Cox-Merz rule. The influence of RIL content in the solvent on apparent viscosities, activation energy, intrinsic viscosities, specific viscosity-c[η] master curve, and relaxation time were also investigated. Gelation occurred in this cellulose solution system due to thermal-induced CO2 release from the decomposition of the CO2-based reversible ionic liquid. The formed gel was stable in air, but re-dissolved when exposed to CO2, indicating the switch-on and switch-off effects of CO2 in cellulose dissolution and gelation.

Preparation of Cellulose Films from Sustainable CO2/DBU/DMSO System.

Cellulose films are regarded as sustainable materials having wide applications in food packaging, separation, etc. Their preparation substantially relies on sufficient dissolution. Herein, various celluloses adequately dissolved in a new solvent system of carbon dioxide,1, 8-diazabicyclo [5.4.0] undec-7-ene and dimethyl sulfoxide (CO2/DBU/DMSO) were made in to films using different regeneration reagents. The films regenerated from ethanol and methanol presented homogeneous and smooth surfaces, while those from 5 wt % NaOH (aq.) and 5 wt % H2SO4 (aq.) showed rough surfaces, as analyzed using scanning electron microscopy (SEM) and atomic force microscopy (AFM). The films regenerated from 5 wt % NaOH (aq.) and 5 wt % H2SO4 (aq.) rendered cellulose II structures, while those regenerated from alcohols had amorphous structures as evidenced using fourier transform infrared spectroscopy (FT-IR) and X-ray diffraction (XRD) results. The films made of microcrystalline cellulose had a good light transmittance of about 90% at 800 nm with a tensile strength of 55 MPa and an elongation break of 6.5%, while those from wood pulp cellulose demonstrated satisfactory flexibility with a tensile strength of 91 MPa and an elongation break of 9.0%. This research reports a simple, environmental, and sustainable method to prepare cellulose films of good mechanical properties.

Fast dissolution pretreatment of the corn stover in gamma-valerolactone promoted by ionic liquids: Selective delignification and enhanced enzymatic saccharification.

The dissolution of corn stover was investigated in gamma-valerolactone (GVL) assisted by ionic liquids. An enhanced subsequent enzymatic saccharification was reached with a total reducing sugar yield of 0.69 g.g-1 and a glucose of 0.38 g.g-1 within 24 h. The treatment effects on the physical-chemical features of corn stover in terms of the natural recalcitrance to the subsequent biological digest were systematically investigated using composition analysis, X-ray diffraction (XRD), scanning electron microscopy (SEM) and atomic force microscopy (AFM). The structures of the associated enzymatic hydrolysis lignin (EHL) and ionic liquid extracted lignin (IEL) were characterized by gel permeation chromatography (GPC), fourier transform infra-red spectroscopy (FTIR), phosphorous nuclear magnet resonance spectrometry (31P NMR), and heteronuclear single quantum coherence spectroscopy (HSQC) for an in-depth understanding of the delignification process and the basic structural information for further lignin valorization.