Chiral separation membranes

Another possibility of constructing a chiral membrane system is to prepare a solution of the chiral selector which is retained between two porous membranes, acting as an enantioselective liquid carrier for the transport of one of the enantiomers from the feed solution of the racemate to the receiving side (Fig. 1-5). This system is often referred to as membrane-assisted separation. The selector should not be soluble in the solvent used for the elution of the enantiomers, whose transport is driven by a gradient in concentration or pH between the feed and receiving phases. As a drawback common to all these systems, it should be mentioned that the transport of one enantiomer usually decreases when the enantiomer ratio in the permeate diminishes. Nevertheless, this can be overcome by designing a system where two opposite selectors are used to transport the two enantiomers of a racemic solution simultaneously, as it was already applied in W-tube experiments [171]. 

L. J. Brice, W. H. Pirkle, Enantioselective transport through liquid membranes in Chiral separations, applications and technology, S. Ahuja (Ed.), American Chemical Society, Washington... 

For the separation of racemic mixtures, two basic types of membrane processes can be distinguished a direct separation using an enantioselective membrane, or separation in which a nonselective membrane assists an enantioselective process [5]. The most direct method is to apply enantioselective membranes, thus allowing selective transport of one of the enantiomers of a racemic mixture. These membranes can either be a dense polymer or a liquid. In the latter case, the membrane liquid can be chiral, or may contain a chiral additive (carrier). Nonselective membranes can also... 

In this chapter we will provide an overview of the application of membrane separations for chiral resolutions. As we will focus on physical separations, the use of membranes in kinetic (bio)resolutions will not be discussed. This chapter is intended to provide an impression, though not exhaustive, of the status of the development of membrane processes for chiral separations. The different options will be discussed on the basis of their applicability on a large scale. 

In general, a liquid membrane for chiral separation contains an enantiospecific carrier which selectively forms a complex with one of the enantiomers of a racemic mixture at the feed side, and transports it across the membrane, where it is released into the receptor phase (Fig. 5-1). 

Feed solution Liquid membrane Receiving solution Fig. 5-1. Schematic representation of a liquid membrane for chiral separation. 

In supported liquid membranes, a chiral liquid is immobilized in the pores of a membrane by capillary and interfacial tension forces. The immobilized film can keep apart two miscible liquids that do not wet the porous membrane. Vaidya et al. [10] reported the effects of membrane type (structure and wettability) on the stability of solvents in the pores of the membrane. Examples of chiral separation by a supported liquid membrane are extraction of chiral ammonium cations by a supported (micro-porous polypropylene film) membrane [11] and the enantiomeric separation of propranolol (2) and bupranolol (3) by a nitrate membrane with a A/ -hexadecyl-L-hydroxy proline carrier [12]. 

Fig. 5-6. Chiral separation by MIP membranes a combination of sieving and selective transport [44],...

Possible applications of MIP membranes are in the field of sensor systems and separation technology. With respect to MIP membrane-based sensors, selective ligand binding to the membrane or selective permeation through the membrane can be used for the generation of a specific signal. Practical chiral separation by MIP membranes still faces reproducibility problems in the preparation methods, as well as mass transfer limitations inside the membrane. To overcome mass transfer limitations, MIP nanoparticles embedded in liquid membranes could be an alternative approach to develop chiral membrane separation by molecular imprinting [44]. 

Nonselective membranes can assist enantioselective processes, providing essential nonchiral separation characteristics and thus making a chiral separation based on enantioselectivity outside the membrane technically and economically feasible. For this purpose several configurations can be applied (i) liquid-liquid extraction based on hollow-fiber membrane fractionation (ii) liquid- membrane fractionation and (iii) micellar-enhanced ultrafiltration (MEUF). 

Novel chiral. separations using enzymes and chiral surfactants as carriers have been realized using facilitated transport membranes. Japanese workers have reported the synthesis of a novel norbornadiene polymeric membrane with optically active pendent groups that show enantio.selectivity, which has shown promi.se in the. separation of propronalol. 

Membranes offer a format for interaction of an analyte with a stationary phase alternative to the familiar column. For certain kinds of separations, particularly preparative separations involving strong adsorption, the membrane format is extremely useful. A 5 x 4 mm hollow-fiber membrane layered with the protein bovine serum albumin was used for the chiral separation of the amino acid tryptophan, with a separation factor of up to 6.6.62 Diethey-laminoethyl-derivatized membrane disks were used for high-speed ion exchange separations of oligonucleotides.63 Sulfonated membranes were used for peptide separations, and reversed-phase separations of peptides, steroids, and aromatic hydrocarbons were accomplished on C18-derivatized membranes. 

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