Immobilizing liquid phase, methods

Methods which enploy liquid phase treating liquors (spray, transfer rolls and belts, etc.) share a cannon difficulty stemming from the lew volume of liquor in relation to the large surface area of the fibers conprising the substrate to be treated. This difficulty is acerbated when aqueous liquors are to be applied to hydrophilic fibers. Foam coating methods enploy stable foams which allow the thickness of the liquid-air mixture to be controlled by a doctor blade or roll. Conparatively low add-ons can be achieved by virtue of the low density of the foam layer, but the stable nature of such foam, and its immobile liquid phase, inhibit rapid, uniform distribution through the substrate. 

Immobilization of catalysts is an important process design feature (see Chapter 9.9). A recent example of catalyst immobilization is the biphasic approach which seems superior to immobilization on solids, as successfully proven in the Ruhrchemie/Rhone Poulenc process for the hydro-formylation of olefins.286 Supported liquid phase catalysis was devised as a method for the immobilization of homogeneous catalysts on solids. When the liquid phase is water, a water-soluble catalyst may be physically bound to the solid. 

An alternative to the supported liquid phase (SLP) method was recently proposed using the same type of solid the supported hydrogen bonded (SHB) catalysts. First demonstrated with the zwitteronic Rh1 catalysts [(sulphos)Rh(cod)] (1) and [(sulphos)Rh(CO)2] (2) (sulphos = 03S(Cr,I I4)CI I2C(CH2PPh2) ). the immobilization procedure is based on the capability of the sulfonate tail of sulphos to link the silanol groups of the support via hydrogen bonds (Figure 12). 

In the method shown in Figure 9A, a biotin-labeled cDNA probe is first immobilized to a polyvinylchloride microtiter plate well that is coated with bio-tinylated-bovine serum albumin [33], The target DNA is hybridized in the liquid-phase with a digoxigenin-labeled probe, so that the biotin-labeled probe can capture a marker enzyme. An antibody-conjugated enzyme is then added, followed by a chemiluminescent substrate. 

The one-pot dynamic kinetic resolution (DKR) of ( )-l-phenylethanol lipase esterification in the presence of zeolite beta followed by saponification leads to (R)-l phenylethanol in 70 % isolated yield at a multi-gram scale. The DKR consists of two parallel reactions kinetic resolution by transesterification with an immobilized biocatalyst (lipase B from Candida antarctica) and in situ racemization over a zeolite beta (Si/Al = 150). With vinyl octanoate as the acyl donor, the desired ester of (R)-l-phenylethanol was obtained with a yield of 80 % and an ee of 98 %. The chiral secondary alcohol can be regenerated from the ester without loss of optical purity. The advantages of this method are that it uses a single liquid phase and both catalysts are solids which can be easily removed by filtration. This makes the method suitable for scale-up. The examples given here describe the multi-gram synthesis of (R)-l-phenylethyl octanoate and the hydrolysis of the ester to obtain pure (R)-l-phenylethanol. 

In simple experiments, particulate silica-supported CSPs having various cin-chonan carbamate selectors immobilized to the surface were employed in an enantioselective liquid-solid batch extraction process for the enantioselective enrichment of the weak binding enantiomer of amino acid derivatives in the liquid phase (methanol-0.1M ammonium acetate buffer pH 6) and the stronger binding enantiomer in the solid phase [64]. For example, when a CSP with the 6>-9-(tcrt-butylcarbamoyl)-6 -neopentoxy-cinchonidine selector was employed at an about 10-fold molar excess as related to the DNB-Leu selectand which was dissolved as a racemate in the liquid phase specified earlier, an enantiomeric excess of 89% could be measured in the supernatant after a single extraction step (i.e., a single equilibration step). This corresponds to an enantioselectivity factor of 17.7 (a-value in HPLC amounted to 31.7). Such a batch extraction method could serve as enrichment technique in hybrid processes such as in combination with, for example, crystallization. In the presented study, it was however used for screening of the enantiomer separation power of a series of CSPs. 

The liquid liquid partition chromatography (LLPQ method involves a stationary liquid phase that is more or less immobilized on a solid support, and a mobile liquid phase. The analyte is therefore distributed between the two liquid phases. In conventional LLPC systems, the stationary liquid phase is usually a polar solvent and the mobile liquid phase is an essentially water-immiscible organic solvent. On the other hand, in reversed-phase chromatography (RPQ, the stationary liquid is usually a hydrophobic... 

For volatile materials vapor phase chromatography (gas chromatography) permits equilibration between the gas phase and immobilized liquids at relatively high temperatures. Tire formation of volatile derivatives, e.g., methyl esters or trimethylsilyl derivatives of sugars, extends the usefulness of the method.103104 A method which makes use of neither a gas nor a liquid as the mobile phase is supercritical fluid chromatography.105 A gas above but close to its critical pressure and temperature serves as the solvent. The technique has advantages of high resolution, low temperatures, and ease of recovery of products. Carbon dioxide, N20, and xenon are suitable solvents. 

Chromatographic methods are divided into two types according to how solute molecules bind to or interact with the stationary phase. Partition chromatography is the distribution of a solute between two liquid phases. This may involve direct extraction using two liquids, or it may use a liquid immobilized on a solid support as in the case of paper, thin-layer, and gas-liquid chromatography. For partition chromatography, the stationary phase... 

Following the work of Bloch and Vofsi, other methods of producing immobilized liquid films were introduced. In one approach, the liquid carrier phase was held by capillarity within the pores of a microporous substrate, as shown in Figure 11.3(a). This approach was first used by Miyauchi [7] and by Largman and Sifniades and others [8,9], The principal objective of this early work was to recover copper, uranium and other metals from hydrometallurgical solutions. Despite considerable effort on the laboratory scale, the first pilot plant was not installed until 1983 [10], The main problem was instability of the liquid carrier phase held in the microporous membrane support. 

Separations in two-phase systems with one immobilized interface(s) are much newer. The first paper on membrane-based solvent extraction (MBSE) published Kim [4] in 1984. However, the inventions of new methods of contacting two and three liquid phases and new types of liquid membranes have led to a significant progress in the last forty years. Separations in systems with immobilized interfaces have begun to be employed in industry. New separation processes in two- and three-phase systems with one or two immobilized L/L interfaces realized with the help of microporous hydrophobic wall(s) (support) are alternatives to classical L/L extraction and are schematically shown in Figure 23.1. Membrane-based solvent extraction (MBSE) in a two-phase system with one immobilized interface feed/solvent at the mouth of microspores of hydrophobic support is depicted in Figure 23.1a and will be discussed... 

The most straightforward immobilization method for catalytically active redox elements for liquid phase oxidation reactions consists of isomorphic substitution. Well-known systems with very peculiar properties that will not be treated in further detail are ... 

Ion partition — The partition coefficients of ions between two liquid phases can be determined with electrochemical methods See ion transfer at liquid-liquid interfaces, and - droplets, electrochemistry of immobilized . 

In the procedures described thus far, the immobile phase was a solid adsorbent. In another procedure, partitio7i chro natography, the immobile phase is an organic liquid adsorbed on a solid. This method resembles extraction in that the solute is partitioned between two liquid phases. However, since the apparatus and procedure used are so similar to those of ordinary chromatography, it will be described here rather than in the next section. The method was originally developed for the separation of acetvdated amino acids and has subsequently been applied to the separation of amino acids themselves, carboxylic acids, carbohydrates, and a number of other types of compounds. One of the more useful separations is that of the carboxylic acids, which will now be described. ... 

Another method used for recycling TSOSs consists in using the so-called supported ionic liquid phase (SILP) [44-49], The general principle is using an OS with a trialkoxysilane moiety that can be grafted covalently to a particle of silica. The particle, now coated with onium salt, has a special affinity for other onium salts, especially ILs. ILs can therefore get immobilized on a solid particle and subsequently be used for immobilizing other reagents (transition metal complexes, proline, etc.). This method has recently been reviewed and employs mostly non-functional ILs, so it won t be explained in more detail [44-49] (Fig. 17). 

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