RESUMEN
Catalytic asymmetric dearomatization (CADA) reactions have evolved into an efficient strategy for accessing chiral polycyclic and spirocyclic scaffolds from readily available planar aromatics. Despite the significant developments, the CADA reaction of naphthalenes remains underdeveloped. Herein, we report a Gd(III)-catalyzed asymmetric dearomatization reaction of naphthalene with a chiral PyBox ligand via visible-light-enabled [4 + 2] cycloaddition. This reaction features application of a chiral Gd/PyBox complex, which regulates the reactivity and selectivity simultaneously, in excited-state catalysis. A wide range of functional groups is compatible with this protocol, giving the highly enantioenriched bridged polycycles in excellent yields (up to 96%) and selectivity (up to >20:1 chemoselectivity, >20:1 dr, >99% ee). The synthetic utility is demonstrated by a 2 mmol scale reaction, removal of directing group, and diversifications of products. Preliminary mechanistic experiments are performed to elucidate the reaction mechanism.
RESUMEN
Polarized holographic properties play an important role in the holographic data storage of traditional organic recording materials. In this study, reduced graphene oxide (RGO) was introduced into a phenanthraquinone-doped polymethylmethacrylate (PQ/PMMA) photopolymer to effectively improve the orthogonal polarization holographic properties of the material. Importantly, the lateral size of RGO nanosheets has an important influence on the polymerization of MMA monomers. To some extent, a larger RGO diameter is more conducive to promoting the polymerization of MMA monomers and can induce more PMMA polymers to be grafted on its surface, thus obtaining a higher PMMA molecular weight. However, too large of a RGO will lead to too much grafting of the PMMA chain to shorten the length of a single PMMA chain, which will lead to the degradation of PQ/PMMA holographic performance. Compared with the original PQ/PMMA, the diffraction efficiency of the RGO-doped PQ/PMMA photopolymer can reach more than 11.4% (more than 3.5 times higher than the original PQ/PMMA), and its photosensitivity is significantly improved by 4.6 times. This study successfully synthesized RGO-doped PQ/PMMA high-performance photopolymer functional materials for multi-dimensional holographic storage by introducing RGO nanoparticles. Furthermore, the polarization holographic properties of PQ/PMMA photopolymer materials can be further accurately improved to a new level.
RESUMEN
Phenanthraquinone-doped polymethyl methacrylate (PQ/PMMA) photopolymers are considered to be the most promising holographic storage media due to their unique properties, such as high stability, a simple preparation process, low price, and volumetric shrinkage. This paper reviews the development process of PQ/PMMA photopolymers from inception to the present, summarizes the process, and looks at the development potential of PQ/PMMA in practical applications.
Asunto(s)
Holografía , Polimetil MetacrilatoRESUMEN
Phenanthrenequinone-doped poly(methyl methacrylate) (PQ/PMMA) photopolymers are potential holographic storage media owing to their high-density storage capacities, low costs, high stability, and negligible shrinkage in volume holographic permanent memory. However, because of the limitations of the substrate, conventional Plexiglas materials do not exhibit a good performance in terms of photosensitivity and molding. In this study, the crosslinked structure of PMMA was modified by introducing a dendrimer monomer, pentaerythritol tetraacrylate (PETA), which increases the photosensitivity of the material 2 times (from ~0.58 cm/J to ~1.18 cm/J), and the diffraction efficiency is increased 1.6 times (from ~50% to ~80%). In addition, the modified material has a superior ability to mold compared to conventional materials. Moreover, the holographic performance enhancement was evaluated in conjunction with a quantum chemical analysis. The doping of PETA resulted in an overall decrease in the energy required for the reaction system of the material, and the activation energy decreased by ~0.5 KJ/mol in the photoreaction stage.
RESUMEN
Temperature plays an important role in anaerobic digestion (AD), and different substrates have different optimum temperatures in AD. However, the effect of temperature on the performance of AD when cellulosic ethanol wastewater was used as a substrate was rarely reported. Therefore, the digestion characteristics of cellulosic ethanol wastewater at 25, 35, 45, and 55 °C were investigated, and the microbial communities of the sludge sample were analyzed after fermentation. The results showed that the cumulative methane production was the highest at 55 °C, 906.40 ± 50.67 mL/g VS, which was 81.06, 72.42, and 13.33% higher than that at 25, 35, and 45 °C, respectively. The content of methane was 68.13, 49.26, 70.46, and 85.84% at the terminal period of fermentation at temperatures of 25, 35, 45, and 55 °C, respectively. The testing of volatile fatty acids (VFAs) indicated that the accumulation of VFAs did not occur when the fermentation was carried out at 25, 35, and 45 °C; however, the VFA content at 55 °C was much larger than that in the three groups (25, 35, and 45 °C), and the ratio of propionic acid to acetic acid was larger than 1.4 at the late stage of fermentation, so it inhibited the fermentation. The diversity of the microbial community indicated that the floral structure and metabolic pathway of fermentation were alike at 25 and 35 °C. Firmicutes and Proteobacteria were the main flora covering the 25-55 °C-based phylum or below it. The relative abundance of Methanosaeta was the highest when fermentation temperatures were 25 and 35 °C; however, its relative abundance decreased sharply and the relative abundance of Methanosarcina increased substantially when the temperature increased from 35 to 45 °C, which indicated that Methanosarcina can exist in higher temperatures. At the same time, hydrogenotrophic methanogens such as Methanoculleus and Methanothermobacter were dominant when fermentation temperatures were 45 and 55 °C, which indicated that the metabolic pathway changed from acetoclastic methanogenesis to hydrogenotrophic methanogenesis.
RESUMEN
It is a promising idea to graft zwitterionic polymers onto lignin and prepare lignin-grafted-poly [2-(methacryloyloxy) ethyl] dimethyl-(3-sulfopropyl) ammonium hydroxide (Lignin-g-PDMAPS) thermosensitive polymer with the upper critical solution temperature (UCST). In this paper, an electrochemically mediated atom transfer radical polymerization (eATRP) method was used to prepare Lignin-g-PDMAPS. The structure and property of the Lignin-g-PDMAPS polymer were characterized by the fourier transform infrared spectrum (FT-IR), nuclear magnetic resonance (NMR), X-ray electron spectroscopy (XPS), dynamic light scattering (DLS), differential scanning calorimeter (DSC). Furthermore, the effect of catalyst structure, applied potential, amount of Lignin-Br, Lignin-g-PDMAPS concentration, NaCl concentration on UCST of Lignin-g-PDMAPS were investigated. It was worth noting that polymerization was well controlled when the ligand was tris (2-aminoethyl) amine (Me6TREN), applied potential was -0.38 V and the amount of Lignin-Br was 100 mg. And the UCST of the Lignin-g-PDMAPS aqueous solution (1 mg/ml) was 51.47 °C, the molecular weight was 8987 g/mol, and the particle size was 318 nm. It was also found that the UCST increased and the particle size decreased with the Lignin-g-PDMAPS polymer concentration increased, and the UCST decreased and the particle size increased with the NaCl concentration increases. This work investigated UCST-thermoresponsive polymer which possessed lignin main chain combining the zwitterionic side chain, and provided a new way for development of lignin based UCST-thermoresponsive materials and medical carrier materials, in addition to expand the scope of eATRP.