Water-organic solvent two-phase systems

By the example of 34 different alkynes, it was convincingly demonstrated that the product of the treatment of [PtCLJ with CO at 40-110 °C is a very powerful alkyne hydration catalyst some of the reactions are shown on Scheme 9.7 [25], The best medium for this transformation is THF containing 5 % H2O. The reaction can also be performed in a water-organic solvent two-phase system (e.g. with 1,2-dichloroethane), however in this case addition of a tetralkylammonium salt, such as Aliquat 336, is required to facilitate mass transfer between the phases. After the reaction with CO, the major part of platinum is present as H2[ Pt3(CO)6 n], but the catalytic effect was assigned to a putative mononuclear Pt-hydride, [PtHCl(CO)2], presumably formed from the cluster and some HCl (supplied by the reduction of [PtCU]). The hydration of terminal acetylenes follows Markovnikov s mle leading exclusively to aldehyde-free ketones. 

Practical preparation is carried out in a water-organic solvent two-phase system as shown in Fig. lib, because both substrate and product strongly inhibit enzyme reactions. Crude extracts from S. salmonicolor after heat- and... 

Despite these problems, water-organic solvent two-phase systems have been successfully used to transform highly lipophilic substrates such as steroids [58],... 

The advantages of using a micellar assembly over a water/organic solvent two-phase system include the following ... 

Table 2 Enzyme-Catalyzed Steroid Transformations in Water-Organic Solvent Two-Phase Systems by Hydroxy Steroid Dehydrogenases (HSDH)... 

Few industrially important bioprocesses are carried out exclusively in organic solvents. Two-phase systems are more common, however, consisting of a water-immiscible solvent that allows adequate dissolution of substrates and products, and an aqueous phase containing the biocatayst.20... 

The inner hydrophobic core of a membrane can be modelled by the use of an organic solvent. Similarly a water or aqueous buffer can be used to mimic the aqueous filled compartment. If the organic solvent is not miscible with water then a two-phase system can be used to study the relative preference of a compound for the aqueous (hydrophiHc) or organic (hydrophobic, lipophilic) phase. 

Often the enzyme stability can be improved by using a suitable water-immiscible solvent instead of a water-miscible one. Two-phase systems are obtained with the enzyme and other hydrophilic substances present in the aqueous phase while hydrophobic substrates and products mainly partition to the organic phase (Figure 9.1). Water immiscible solvents often used for enzymatic reactions are hydrocarbons, ethers and esters further details on solvents are found in the section 9.5 Selection of solvents , below. In order for the bioconversion to occur, the substrates must be transferred to the enzyme in the aqueous phase after the reaction hydrophobic... 

Furthermore, FSA tolerates organic co-solvents such as DMF (10-20% v/v), acetonitrile (10-20% v/v), ethanol (20%), and even a water/ethyl acetate two-phase system. 

In a two-phase system (Figure 2.5c), the organic (water immiscible) solvent may be used as product extractant. In addition, recirculation of the organic phase can serve to transfer oxygen and to mix the aqueous phase. 

The volumetric ratio of the two liquid phases (j6 = Forg/ Faq) can affect the efficiency of substrate conversion in biphasic media. The biocatalyst stability and the reaction equilibrium shift are dependent on the volume ratio of the two phases [29]. In our previous work [37], we studied the importance of the nonpolar phase in a biphasic system (octane-buffer pH 9) by varying the volume of solvent. The ratio /I = 2/10 has been the most appropriate for an improvement of the yield of the two-enzyme (lipase-lipoxygenase) system. We found that a larger volume of organic phase decreases the total yield of conversion. Nevertheless, Antonini et al. [61] affirmed that changes in the ratios of phases in water-organic two-phase system have little effect upon biotransformation rate. 

For long chain olefins, the hydroformylation generally proceeds slowly and with low selectivity in two-phase systems due to their poor solubility in water. Monflier et al. recently reported a conversion of up to 100% and a regioselectivity of up to 95% for the Rh-catalyzed hydroformylation of dec-l-ene in water, free of organic solvent, in the presence of partially methylated 6-cyclodextrins (Eq. 3.42).173... 

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