Organic solvents solvent engineering

For the GC analysis of (semi)volatile organic compounds, usually flame ionization detection (FID) or electron capture detection (ECD) (for halogenated compounds) offer sufficient sensitivity. Complex mixtures of organics do not always result In baseline separation of the individual contaminants as is the case for organic solvent mixtures, engine fuel vapors, or emissions from combustion processes. Also, the matrix may cause poor peak quality in the chromatographic separation. In these cases, MS can offer the selectivity to compensate for these limitations. 

Noryl is a rigid dimensionally stable material. Dimensional stabiUty results from a combination of low mold shrinkage, low coefficient of thermal expansion (5.9 x 10 per° C), good creep resistance (0.6—0.8% in 300 h at 13.8 MPa (2000 psi)), and the lowest water absorption rate of any of the engineering thermoplastics (0.07% in 24 h at room temperature). Noryl resins are completely stable to hydrolysis. They are not affected by aqueous acids or bases and have good resistance to some organic solvents, but they are attacked by aromatic or chlorinated aUphatic compounds. 

Obviously, there are many good reasons to study ionic liquids as alternative solvents in transition metal-catalyzed reactions. Besides the engineering advantage of their nonvolatile natures, the investigation of new biphasic reactions with an ionic catalyst phase is of special interest. The possibility of adjusting solubility properties by different cation/anion combinations permits systematic optimization of the biphasic reaction (with regard, for example, to product selectivity). Attractive options to improve selectivity in multiphase reactions derive from the preferential solubility of only one reactant in the catalyst solvent or from the in situ extraction of reaction intermediates from the catalyst layer. Moreover, the application of an ionic liquid catalyst layer permits a biphasic reaction mode in many cases where this would not be possible with water or polar organic solvents (due to incompatibility with the catalyst or problems with substrate solubility, for example). 

Biocatalysts in nature tend to be optimized to perform best in aqueous environments, at neutral pH, temperatures below 40 °C, and at low osmotic pressure. These conditions are sometimes in conflict with the need of the chemist or process engineer to optimize a reaction with respect to space-time yield or high product concentration in order to facilitate downstream processing. Furthermore, enzymes and whole cells are often inhibited by products or substrates. This might be overcome by the use of continuously operated stirred tank reactors, fed-batch reactors, or reactors with in situ product removal [14, 15]. The addition of organic solvents to increase the solubility of substrates and/or products is a common practice [16]. 

Polycarbonates (PC) are another group of condensation thermoplastics used mainly for special engineering purposes. These polymers are considered polyesters of carbonic acid. They are produced by the condensation of the sodium salt of bisphenol A with phosgene in the presence of an organic solvent. Sodium chloride is precipitated, and the solvent is removed by distillation ... 

The specificity of enzyme reactions can be altered by varying the solvent system. For example, the addition of water-miscible organic co-solvents may improve the selectivity of hydrolase enzymes. Medium engineering is also important for synthetic reactions performed in pure organic solvents. In such cases, the selectivity of the reaction may depend on the organic solvent used. In non-aqueous solvents, hydrolytic enzymes catalyse the reverse reaction, ie the synthesis of esters and amides. The problem here is the low activity (catalytic power) of many hydrolases in organic solvents, and the unpredictable effects of the amount of water and type of solvent on the rate and selectivity. 

The term medium engineering , that is the possibility to affect enzyme selectivity simply by changing the solvent in which the reaction is carried out, was coined by Klibanov, who indicated it as an alternative or an integration to protein engineering [5aj. Indeed, several authors have confirmed that the enantio-, prochiral-, and even regioselectivity of enzymes can be influenced, sometimes very remarkably, by the nature of the organic solvent used. 

NWUHA v (2000) Novel studies on membrane extraction of bioactive components of green tea in organic solvents part I , J Food Engineering, 44 (4), 233-8. 

Chitosan has found many biomedical applications, including tissue engineering approaches. Enzymes such as chitosanase and lysozyme can degrade chitosan. However, chitosan is easily soluble in the presence of acid, and generally insoluble in neutral conditions as well as in most organic solvents due to the existence of amino groups and the high crystallinity. Therefore, many derivatives have been reported to enhance the solubility and processability of this polymer. 

The term fluorous was coined as an analogy to aqueous for highly fluorinated alkanes, ethers and tertiary amines [1], These compounds differ markedly from the corresponding hydrocarbon compounds to the extent that such compounds commonly give bilayers with conventional organic solvents. In this chapter, we will discuss the different approaches towards carrying out reactions in fluorous media and describe how reactants and catalysts can be engineered to be preferentially soluble in fluorous solvents. 

The use of water-miscible organic solvent-water mixtures is a particularly attractive method for use with cofactor-dependent enzymes due to its simphcity. The high water content can allow dissolution of both enzyme and cofactor, whilst the water-miscible solvent can provide a dual role in both substrate dissolution and as a cosubstrate for cofactor recycling (substrate-coupled cofactor recycling).The asymmetric reduction of a ketone intermediate of montelukast using an engineered ADH in the presence of 50 % v/v isopropanol offers a powerful demonstration of this methodology (Scheme 1.55). 

Efficient biocatalysis in neat organic solvent depends on the careful choice of the method of dehydrated enzyme preparation and solvent used. Optimization of these factors towards a given transformation is often known as catalyst formulation and solvent, or medium, engineering respectively, both of which will be briefly discussed below. Catalyst engineering which also provides a powerful method of improving activity and stability, is discussed in Chapter 2. 

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