D-Valine

D-Valine is an important organic chiral source and has extensive industrial application, which is used as intermediate for the synthesis of agricultural pesticides, semi-synthetic veterinary antibiotics and pharmaceutical drugs. Its derivatives have shown great activity in clinical use, such as penicillamine for the treatment of immune-deficiency diseases, and actinomycin D for antitumor therapy. Fluvalinate, a pyrethroid pesticide made from D-valine, is a broad-spectrum insecticide with low mammalian toxicity. Valnemulin, a semi-synthetic pleuromutilin derivative synthesized from D-valine, is an antibiotic for animals. Moreover, D-valine is also used in cell culture for selectively inhibiting fibroblasts proliferation. Due to its widespread application, D-valine is gaining more and more attention and some approaches for D-valine preparation have been investigated. In comparison with other approaches, microbial preparation of D-valine is more competitive and promising because of its high stereo selectivity, mild reaction conditions and environmental friendly process. So far, microbial preparation of D-valine can be mainly classified into three categories: microbial asymmetric degradation of DL-valine, microbial stereoselective hydrolysis of N-acyl-DL-valine by D-aminoacylase, and microbial specific hydrolysis of DL-5-isopropylhydantoin by D-hydantoinase coupled with D-carbamoylase. In this paper, the industrial application of D-valine and its microbial preparation are reviewed.

To develop a practical process for D-valine preparation from DL-valine, L-valine was used as a sole source of carbon and nitrogen in basal minimal medium to isolate L-valine-degrading micro-organisms. A yeast strain DLPU-zpb was obtained, which showed asymmetric degrading activity against DL-valine. Based on the morphology, physiological and biochemical characteristics, and 26S rDNA D1/D2 domain sequence, strain DLPU-zpb was identified as Candida maltosa. The cells of this strain were used as a biocatalyst for eliminating the L-isomer from DL-valine. The L-isomer was completely degraded within 72 h under the conditions of 30°C, pH control at 6·0, 200 rev min(-1) and 50 g l(-1) DL-valine. The strain DLPU-zpb degraded L-valine effectively but not D-valine, and thus D-valine could be easily isolated from the resultant reaction mixture, which provides a new method for D-valine preparation from DL-valine.Significance and impact of the study:D-valine is an important raw material for medicines and its demand is increasing year by year. Several approaches for D-valine preparation have been reported, but none of them are likely to provide product at low cost. A newly isolated L-valine-degrading yeast strain Candida maltosa DLPU-zpb was described, which showed asymmetric degrading activity against DL-valine. Thus, a new and practical process for D-valine preparation from DL-valine could be developed. This is the first report of the asymmetric degrading ability of C. maltosa against DL-valine and D-valine preparation from DL-valine.

Adsorption kinetic studies are conducted to investigate the potential to use chiral mesoporous materials nanoporous guanosine monophosphate material-1 (NGM-1) and nanoporous folic acid material-1 (NFM-1) for the enantiomeric separation of l- and d-valine. A pseudo-second-order (PSO) kinetic model is applied to test the experimental adsorption equilibrium isotherms, according to both the Langmuir and Freundlich models and the characteristic parameters for each model are determined. The calcined versions of both NGM-1 and NFM-1 fit the Langmuir model with maximum sorption capacities of 0.36 and 0.26 g/g for the preferred adsorption enantiomers, d-valine and l-valine, respectively. Experimental results and the analysis of adsorption models suggest a strong adsorbate-adsorbent interaction, and the formation of a monolayer of tightly packed amino acid on the internal mesopore surface for the preferred enantiomers.