Enantioselective chiral sorption of 1-phenylethanol by homochiral 1D coordination polymers

Enantioselective resolution by coordination polymers has the potential to provide a high degree of discrimination by virtue of well-defined pores and the possibilty of identifying and modifying binding sites. Differences...

Characterization of an Immobilized Amino Acid Racemase for Potential Application in Enantioselective Chromatographic Resolution Processes

Enantioselective resolution processes can be improved by integration of racemization. Applying environmentally friendly enzymatic racemization under mild conditions is in particular attractive. Owing to the variety of enzymes and the progress in enzyme engineering, suitable racemases can be found for many chiral systems. An amino acid racemase (AAR) from P. putida KT2440 is capable of processing a broad spectrum of amino acids at fast conversion rates. The focus of this study is the evaluation of the potential of integrating ARR immobilized on Purolite ECR 8309 to racemize L- or D-methionine (Met) within an enantioselective chromatographic resolution process. Racemization rates were studied for different temperatures, pH values, and fractions of organic co-solvents. The long-term stability of the immobilized enzyme at operating and storage conditions was found to be excellent and recyclability using water with up to 5 vol% ethanol at 20 °C could be demonstrated. Packed as an enzymatic fixed bed reactor, the immobilized AAR can be coupled with different resolution processes; for instance, with chromatography or with preferential crystallization. The performance of coupling it with enantioselective chromatography is estimated quantitatively, exploiting parametrized sub-models. To indicate the large potential of the AAR, racemization rates are finally given for lysine, arginine, serine, glutamine, and asparagine.

Enantioselective Resolution of (R, S)-DMPM by a Adsorption-Covalent Crosslinked Esterase PAE07 from Pseudochrobactrum Asaccharolyticum WZZ003

(R)-N-(2,6-dimethylphenyl) alanine ((R)-MAP-acid) is an important chiral intermediate of the Fungicide (R)-Metalaxyl. In this study, ten kinds of immobilized resins(XAD1180N, H103, HAD7HP, D3520, NKA, D101 , DM11,850 JinKai, Primary amino resin and 850 synthetic resin) were used to adsorption-covalent crosslinked esterase PAE07 for splitting (R, S)-DMPM. The resin D3520 with porous structure and hydrophobic polystyrene was selected for immobilization as the carrier, after optimization of the immobilization conditions, the enzyme load is 20:1 (mg/g), the adsorption time is 4h, and the adsorption buffer pH is 7.0 . The Km and Vmax of the free esterases were 35.66 mM and 4.46 mM/mg·min, respectively, The Km and Vmax of the immobilized PAE07 were 19.05 mM and 2.84 mM/mg·min. The SEM analysis showed that the immobilized esterase PAE07 had higher thermal stability, pH stability and substrate specifity than those from the free esterase. Under the optimal conditions,the reaction was carried out at 35°C and 200 rpm for resolution of 350 mM substrate for 14 hours, the conversion rate reached 48%, and the e.e.p was 99.5%.The repeatability of immobilized esterase PAE07 was evaluated by continuous catalytic resolution of (R, S)-DMPM. The results showed that after 15 times of repeated use, 86.2% of the relative enzyme activity was retained. These results proved that immobilized esterase PAE07 as a new catalyst had great potential for the application and industrial enzymatic resolution of (R, S)-DMPM to prepare (R)-metalaxyl.

Strategy for Polymorphic Control by Enzymatic Reaction and Antisolvent Crystallization: Effect of Aminoacylase on Metastable β-Glycine Formation

Although the enantioselective resolution by aminoacylase has been established for a long time, the effect of aminoacylase on the amino acid polymorphism is still unclear. To explore whether the presence...

Chiral Mesoporous Silica Materials: A Review on Synthetic Strategies and Applications

Because of its tunable textural properties and chirality feature, chiral mesoporous silica (CMS) gained significant consideration in many fields and has been developed rapidly in recent years. In this review, we provide an overview of synthesis strategies for fabricating CMS together with its main applications. The properties of CMS, including morphology and mesostructures and enantiomer excess (ee), can be altered according to the synthetic conditions during the synthesis process. Despite its primary stage, CMS has attracted extensive attention in many fields. In particular, CMS nanoparticles are widely used for enantioselective resolution and adsorption of chiral compounds with desirable separation capability. Also, CMS acts as a promising candidate for the effective delivery of chiral or achiral drugs to produce a chiral-responsive manner. Moreover, CMS also plays an important role in chromatographic separations and asymmetric catalysis. There has been an in-depth review of the synthetic methods and mechanisms of CMS. And this review aims to give a deep insight into the synthesis and application of CMS, especially in recent years, and highlights the significance that it may have in the future.

Biodegradation of 1,2,3-Trichloropropane to Valuable (S)-2,3-DCP Using a One-Pot Reaction System

1,2,3-trichloropropane (TCP) being one of the important environmental pollutants, has drawn significant concern due to its highly toxic and carcinogenic effects. In this study, we built a one-pot reaction system in which immobilized haloalkane dehalogenase (DhaA31) and halohydrin dehalognase (HheC) were used to catalyze the recalcitrant TCP to produce 2,3-dichloro-1-propanol (2,3-DCP) by removing epichlorohydrin (ECH). Since HheC displays a high R enantiopreference toward 2,3-DCP, the production of enantiopure (S)-2,3-DCP was expected. However, the enantioselective resolution of (R,S)-2,3-DCP by HheC was greatly inhibited by the circular reaction occurring between the product ECH and 1,3-dichloro-2-propanol (1.3-DCP). To resolve this problem, HZD-9 resin-based in situ product removal was implemented. Under the optimized conditions, TCP was completely consumed, resulting in optically pure (S)-2,3-DCP with enantiomer excess (e.e) > 99% and 40% yield (out of the 44% theoretical maximum). The scale-up resin-integrated reaction system was successfully carried out in 0.5 L batch reactor. Moreover, the system could be reused for 6 rounds with 64% of original activity retained, showing that it could be applied in the treatment of large volumes of liquid waste and producing enantiopure (S)-2,3-DCP.