Cross-polarization with magic-angle spinning kinetics and impedance spectroscopy study of proton mobility,local disorder,and thermal equilibration in hydrogen-bonded poly(methacrylic acid)

The ¹H–¹³C cross-polarization with magic-angle spinning (CP MAS) kinetics was studied in poly(methacrylic acid) (PMAA) having the purpose to track the links between the local order in the main chain and the proton dynamics in peripheral hydrogen bond networks. The experimental CP MAS kinetic curves were analyzed applying the models of isotropic and anisotropic spin-diffusion with thermal equilibration. The fractal dimension D_p ≈ 3 was deduced that indicates that PMAA behaves as an isotropic 3D-system. No proton conductivity in the neat PMAA was deduced from the impedance spectroscopy data analyzing the frequency dependences of the complex dielectric permittivity. The value of local order parameter S = 0.70 for CH₂ in PMAA occupies an intermediate position between 0.63 and 0.85 deduced for CH₂ sites in the main chains of poly(vinyl phosphonic acid) and poly(2-hydroxyethyl methacrylate), that is, the true proton conductor and the polymer that contains the H-bond network, however, no proton conductivity, respectively.     

First total synthesis and reassignment of absolute configuration of diosniponol A and B

Enantioselective first total synthesis of diosniponol A and B has been achieved starting from commercially available vanillin. Wittig reaction, Keck allylation, and Prins cyclization reactions are the key steps involved in the target synthesis.     

Optimization of technological parameters of the process for obtaining bisphenols on cation-exchange catalyst in the presence of hydrogen sulfide

Method for synthesis of bisphenols on a solid cation-exchange catalyst in the presence of hydrogen sulfide was optimized with respect to the main technological parameters. This method provides high yields of bisphenols obtained both on the basis of acetone and in the case of complex sterically hindered ketones: 9-fluorenone and dihydroisophorone.     

Removal of Water-Soluble Extractives Improves the Enzymatic Digestibility of Steam-Pretreated Softwood Barks

Softwood bark contains a large amounts of extractives—i.e., soluble lipophilic (such as resin acids) and hydrophilic components (phenolic compounds, stilbenes). The effects of the partial removal of water-soluble extractives before acid-catalyzed steam pretreatment on enzymatic digestibility were assessed for two softwood barks—Norway spruce and Scots pine. A simple hot water extraction step removed more than half of the water-soluble extractives from the barks, which improved the enzymatic digestibility of both steam-pretreated materials. This effect was more pronounced for the spruce than the pine bark, as evidenced by the 30 and 11% glucose yield improvement, respectively, in the enzymatic digestibility. Furthermore, analysis of the chemical composition showed that the acid-insoluble lignin content of the pretreated materials decreased when water-soluble extractives were removed prior to steam pretreatment. This can be explained by a decreased formation of water-insoluble “pseudo-lignin” from water-soluble bark phenolics during the acid-catalyzed pretreatment, which otherwise results in distorted lignin analysis and may also contribute to the impaired enzymatic digestibility of the barks. Thus, this study advocates the removal of extractives as the first step in the processing of bark or bark-rich materials in a sugar platform biorefinery.     

Electrically Conductive Composites Based on Chitosan and Graphene Stabilized by Pluronic F-108

Highly concentrated dispersions of few-layer graphene stabilized by amphiphilic block copolymer Pluronic F-108 are obtained. According to transmission electron and atomic force microscopy, the thickness of the graphene particles is on average from one to ten layers and their lateral sizes vary from 150 nm to 1 μm. Using these dispersions, new chitosan-based film composites with the filler content up to 5 wt % are obtained; the electrical conductivity of these composites reaches 4.3 × 10^–1 S/cm.