Diastereoselective Heterogeneous Catalytic Hydrogenation of Aromatic or Heteraromatic Compounds

The diastereoselective hydrogenation catalyzed by heterogeneous metallic catalysts uses a covalently bound chiral auxiliary to induce the chirality. It remains an active synthetic methodology in the asymmetric synthesis of chiral products and may proceed with high diastereoselectivity. This review describes recent examples using this method, such as hydrogenation of C=C, C=O, and C=N bonds. The use of a chiral auxiliary group has also been successfully applied to the hydrogenation of aromatic and heteroaromatic rings. The choice of the chiral auxiliary was found to play a key role in the asymmetric hydrogenation. The results could be explained in terms of steric effect, with a preferred conformation of the adduct substrate and the addition occurring from the less bulky side. The catalytic metal, the support and the presence of additives were also found to have a significant influence.     

Superheated Steam Drying: An Overview of Pilot and Industrial Dryers with a Focus on Energy Efficiency

According to the principle of sustainability, modern industry should preserve nonrenewable energy sources and develop more efficient processes, especially in terms of energy consumption. The depletion of fossil energy reserves, the environmental impact of greenhouse gases, and the possible threats of environmental taxes are the main reasons to develop new processes in general, and new drying processes in particular, for the existing industries. Using superheated steam as a drying medium instead of hot air can improve the energy efficiency by reusing the energy from exhausted steam and prevent gas emission into the atmosphere by condensation. The present review is focused on both lab-scale pilots—including impingement jet, fluid bed, kiln, fixed bed, and flash drying—described in the literature and existing industrial facilities, with a specific analysis focused on energy efficiency. The usefulness of superheated steam drying pilots for experimental research and for the design of industrial dryers is analyzed. The impact on quality specifications of the dried product for different operating conditions is also presented. Documentation on industrial superheated steam dryers is very rare. Nevertheless, this work presents and analyses the key data available for superheated steam drying of beet, alfalfa, industrial pulp, and paint sludge. Energy recovery and process integration, with a focus on specific technological challenges for industrial dryer implementation, are also presented. This document will result in a discussion of some new ideas for possible R&D in superheated steam drying.     

Thioacidolysis of Lignin: Comparison with Acidolysis

Abstract

Arylglycerol-ether bonds of lignin samples or model compounds vera selectively cleaved by treatment with dioxane-ethanethiol (9/1, v/v) and 0.2 N HBF₄ etherate or 0.2 N BF₃ etherate at 100°C for four hour3. Monomers resulting from “thioacidolysis” were identified by gas chroraatography-mass spectrometry of their trimethylslly derivatives. Compared to acidolysls (dloxane-water, 0.2 N HCL, 100°C 4h), thioacidolysis yields less complex mixtures of monomers. The monomer yields for lignin thioacidolysis were also higher than for acidolysls. This increase was particularly evident for hardwood lignins.     

Performance of exterior semitransparent PVDF–acrylic coatings

The purpose of this study was to investigate the performance of a semitransparent PVDF–acrylic coating on two wood species: Black spruce and White pine. An accelerated aging test was performed on the PVDF–acrylic coating and the results obtained were compared with those obtained for a water-based acrylic coating. Color changes were found to be more significant for the acrylic coating, especially after 1000 h of exposure, and for the White pine panels. Infrared spectroscopy revealed that the acrylic resin was more affected by the accelerated aging test than the PVDF resin, although X-ray photoelectron spectroscopy revealed that PVDF was slightly affected at the extreme surface (first 10 nm). Star-shaped defects were found at the surface of the White pine panels finished with the PVDF–acrylic coating. Experiments revealed that the PVDF–acrylic coating does not seem to be flexible enough to sustain resin exudation or other stresses.     

Structure and Reactivity of Spruce Mechanical Pulp Lignins Part I. Bleaching and Photoyellowing of in situ Lignins

This paper reports the structural investigation of a series of in situ spruce lignins in wood, thermomechanical pulp (TMP) and the corresponding bleached (BTMP) and photoyellowed (YBTMP) samples. This was achieved by using an original two-step degradative technique, thioacidolysis followed by Raney nickel desulfuration. The determination of thioacidolysis monomeric and dimeric products allowed an estimate of various lignin building units and interunit bonds, respectively. It was observed that the thermomechanical and bleaching treatments did not affect spruce lignin structure to an appreciable extent. On the contrary, the photoyellowing treatment caused marked structural changes in lignin, particularly when run in severe conditions. These changes were essentially a decrease in the amount of β-O-4 and β-1 interunit bonds and a relative increase in catechol units and in vanillin end-groups.     

Recent advances on ion-imprinted polymers

Selective recognition of metal ions is a real challenge for a large range of applications in the analytical field (from extraction to detection and quantification). For that purpose, ion-imprinted polymers (IIPs) have been increasingly developed during the last 15 years on the principle of molecularly imprinted polymers (MIPs). Those imprinted materials are designed to mimic the binding sites of biological entities and assure an improved recognition of the template species. The aim of this review is to give the current state of the art in the conception of IIPs from the components to the polymerization process. Some applications of those materials will be also discussed.     

Implicit Bayesian Inference Using Option Prices

Abstract. A Bayesian approach to option pricing is presented in which posterior inference about the underlying returns process is conducted implicitly via observed option prices. A range of models allowing for conditional leptokurtosis, skewness and time‐varying volatility in returns are considered, with posterior parameter distributions and model probabilities backed out from the option prices. Models are ranked according to several criteria, including out‐of‐sample predictive and hedging performance. The methodology accommodates heteroscedasticity and autocorrelation in the option pricing errors, as well as regime shifts across contract groups. The method is applied to intraday option price data on the S&P500 stock index for 1995. While the results provide support for models that accommodate leptokurtosis and skewness, no one model dominates when all criteria are considered.     

Discovery of Highly Potent Dual Orexin Receptor Antagonists via a Scaffold‐Hopping Approach

Starting from suvorexant (trade name Belsomra), we successfully identified interesting templates leading to potent dual orexin receptor antagonists (DORAs) via a scaffold‐hopping approach. Structure–activity relationship optimization allowed us not only to improve the antagonistic potency on both orexin 1 and orexin 2 receptors (Ox1 and Ox2, respectively), but also to increase metabolic stability in human liver microsomes (HLM), decrease time‐dependent inhibition of cytochrome P450 (CYP) 3A4, and decrease P‐glycoprotein (Pgp)‐mediated efflux. Compound 80 c [{(1S,6R)‐3‐(6,7‐difluoroquinoxalin‐2‐yl)‐3,8‐diazabicyclo[4.2.0]octan‐8‐yl}(4‐methyl‐[1,1′‐biphenyl]‐2‐yl)methanone] is a potent and selective DORA that inhibits the stimulating effects of orexin peptides OXA and OXB at both Ox1 and Ox2. In calcium‐release assays, 80 c was found to exhibit an insurmountable antagonistic profile at both Ox1 and Ox2, while displaying a sleep‐promoting effect in rat and dog models, similar to that of the benchmark compound suvorexant.