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Highly efficient asymmetric reduction of 2-octanone to (R)-2-octanol catalyzed by immobilized Acetobacter sp. CCTCC M209061 cells was achieved in a biphasic system. Bioreduction conducted in aqueous single phase buffer was limited due to poor solubility and toxicity towards cells cause by product accumulation. Introduction of [C 4 MIM]·Ac accelerated the biotransformation process, giving 99% yield, >99% product e.e. and 1.42-fold higher initial reaction rate in conversion of 10 mM 2-octanone as substrate, compared with 99% yield, 97.3% product e.e. and 1.57 μmol min -1 of initial reaction rate in a aqueous single phase buffer system containing 6 mM 2-octanone as the optimal substrate concentration. Moreover, in the [C 4 MIM]·Ac-containing buffer/n-tetradecane biphasic system, the optimal substrate concentration was enhanced by 83 times (500 mM) in comparison with that in aqueous single phase buffer, resulting in 53.4% yield (267 mM), 99% product e.e. with 8.9 mM g -1  h -1 space time yield., (Copyright © 2019 Elsevier B.V. All rights reserved.)

This study demonstrated a novel method for determining the melting point (MP) of industrial grade alkyl ketene dimer (AKD) wax by an automated headspace gas chromatographic (HS-GC) technique, in which methanol was used as the tracer. It was based on measuring the GC signal of methanol released from an aqueous solution during the temperature increasing. When the temperature of AKD MP reached, the AKD granules floated on the surface aqueous solution was liquidized and completely isolated the methanol transfer from the solution to the headspace. Thus, a transition point, corresponding to the MP of AKD wax, was observed when plotting the GC signal of methanol vs. the temperature. The results showed that the method has a good measurement precision (RSD < 0.68%) and accuracy (the relative differences were < 7.16%, compared to a reference method). The present method is simple, accurate and particularly suitable to be used in the batch sample testing. This new measurement concept can be also adopted to many related applications., (Copyright © 2018 Elsevier B.V. All rights reserved.)

This paper reports on an ionic-liquid assisted headspace gas chromatographic (HS-GC) for the determination of the content of alkyl ketene dimer (AKD) in its latex samples, in which the GC system was equipped with a thermal conductivity detector (TCD). The method was based on the AKD hydrolysis conducted in 1-butyl-3-methylimidazolium chloride (ionic-liquid) added medium at 100°C for 10min in a closed headspace sample vial, and the measured CO 2 (the resulting product of the hydrolysis) by HS-GC. The results showed that the present method has a good measurement precision (RSD <2.3%) and accuracy (recoveries from 96 - 105%), and the limit of quantitation (LOQ) is 0.9%. The present method is very suitable to be used for the routine check of AKD content in its latex sample in mill applications. The study also showed that the content of AKD in the tested commercial latex samples were in the range of 3.5-12%., (Copyright © 2017 Elsevier B.V. All rights reserved.)

Causticized calcium carbonate (CCC), a solid waste derived from kraft black recovery process, can be used as an alternative for the conventional precipitated calcium carbonate (PCC). However, the application of the CCC has been limited due to its low sizing efficiency in its filled paper. In this study, the characteristics of the CCC were studied aiming to improve the alkyl ketene dimer (AKD) sizing performances of the CCC filled papers, and the results were compared with those from PCC filled papers. The results showed that the CCC had higher pore structure, higher specific surface area, and more negative charge density than the PCC, thus leading to a higher cationic AKD adsorption onto the CCC filler. The lower AKD sizing efficiency in the CCC filled paper can be explained by the combination of higher AKD adsorption and migration, both of which resulted in preferred AKD adsorption onto/into the CCC fillers, rather than the cellulose fibers. Based on the above, the prior addition of polyamide-polyamine epichlorhydrin (PAE) resin to the CCC filler system was proposed to remedy the related issues, thus improving the sizing efficiency.

The efficient anti-Prelog asymmetric reduction of 2-octanone with Acetobacter pasteurianus GIM1.158 cells was successfully performed in a biphasic system consisting of deep eutectic solvent (DES) and water-immiscible ionic liquid (IL). Various DESs exerted different effects on the synthesis of (R)-2-octanol. Choline chloride/ethylene glycol (ChCl/EG) exhibited good biocompatibility and could moderately increase the cell membrane permeability thus leading to the better results. Adding ChCl/EG increased the optimal substrate concentration from 40 mM to 60 mM and the product e.e. kept above 99.9%. To further improve the reaction efficiency, water-immiscible ILs were introduced to the reaction system and an enhanced substrate concentration (1.5 M) was observed with C4MIM·PF6. Additionally, the cells manifested good operational stability in the reaction system. Thus, the efficient biocatalytic process with ChCl/EG and C4MIM·PF6 was promising for efficient synthesis of (R)-2-octanol.

In this study, we employed nanocrystalline cellulose (NCC) as an efficient dispersant to perpare alkyl ketene dimer (AKD) emulsion. The particle size and zeta potential of AKD/NCC emulsion were measured, which were approximately 5 μm and -50 mV, respectively. The surface-sized paper possessed multiple barriers properties. The air permeability of surface-sized paper was 0.29 μm/Pas and the sizing degree reached 42 s when the amount of sizing was 12.58 g/m(2) with a 96.83% decrease and a 40.00%, increase, respectively. Furthermore, the mechanical properties were optimal when the amount of sizing was about 8 g/m(2). AKD/NCC emulsion acted as a good reinforcing agent in surface-sized paper., (Copyright © 2015 Elsevier Ltd. All rights reserved.)

A novel carbonyl reductase (AcCR) catalyzing the asymmetric reduction of ketones to enantiopure alcohols with anti-Prelog stereoselectivity was found in Acetobacter sp. CCTCC M209061 and enriched 27.5-fold with an overall yield of 0.4% by purification. The enzyme showed a homotetrameric structure with an apparent molecular mass of 104 kDa and each subunit of 27 kDa. The gene sequence of AcCR was cloned and sequenced, and a 762 bp gene fragment was obtained. Either NAD(H) or NADP(H) can be used as coenzyme. For the reduction of 4'-chloroacetophenone, the Km value for NADH was around 25-fold greater than that for NADPH (0.66 mM vs 0.026 mM), showing that AcCR preferred NADPH over NADH. However, when NADH was used as cofactor, the response of AcCR activity to increasing concentration of 4'-chloroacetophenone was clearly sigmoidal with a Hill coefficient of 3.1, suggesting that the enzyme might possess four substrate-binding sites cooperating with each other The Vmax value for NADH-linked reduction was higher than that for NADPH-linked reduction (0.21 mM/min vs 0.17 mM/min). For the oxidation of isopropanol, the similar enzymological properties of AcCR were found using NAD+ or NADP+ as cofactor. Furthermore, a broad range of ketones such as aryl ketones, α-ketoesters and aliphatic ketones could be enantioselectively reduced into the corresponding chiral alcohols by this enzyme with high activity.

Background: The bacterium Acetobacter sp. CCTCC M209061 is a promising whole-cell biocatalyst with exclusive anti-Prelog stereoselectivity for the reduction of prochiral ketones that can be used to make valuable chiral alcohols such as (R)-4-(trimethylsilyl)-3-butyn-2-ol. Although it has promising catalytic properties, its stability and reusability are relatively poor compared to other biocatalysts. Hence, we explored various materials for immobilizing the active cells, in order to improve the operational stability of biocatalyst., Results: It was found that Ca-alginate give the best immobilized biocatalyst, which was then coated with chitosan to further improve its mechanical strength and swelling-resistance properties. Conditions were optimized for formation of reusable immobilized beads which can be used for repeated batch asymmetric reduction of 4'-chloroacetophenone. The optimized immobilized biocatalyst was very promising, with a specific activity of 85% that of the free-cell biocatalyst (34.66 μmol/min/g dw of cells for immobilized catalyst vs 40.54 μmol/min/g for free cells in the asymmetric reduction of 4'-chloroacetophenone). The immobilized cells showed better thermal stability, pH stability, solvent tolerance and storability compared with free cells. After 25 cycles reaction, the immobilized beads still retained >50% catalytic activity, which was 3.5 times higher than degree of retention of activity by free cells reused in a similar way. The cells could be recultured in the beads to regain full activity and perform a further 25 cycles of the reduction reaction. The external mass transfer resistances were negligible as deduced from Damkohler modulus Da < <1, and internal mass transfer restriction affected the reduction action but was not the principal rate-controlling step according to effectiveness factors η < 1 and Thiele modulus 0.3<∅ <1., Conclusions: Ca-alginate coated with chitosan is a highly effective material for immobilization of Acetobacter sp. CCTCC M209061 cells for repeated use in the asymmetric reduction of ketones. Only a small cost in terms of the slightly lower catalytic activity compared to free cells could give highly practicable immobilized biocatalyst.