Poly chiral centers containing

First, the short chain length PHAs, poly(HASCL), are composed of monomeric units containing up to 5 carbon atoms. The most well-known representatives are poly(3-hydroxybutyrate) (PHB), and its copolymers with hydroxyvalerate. Of all the PHAs, PHB is by far the most commonly encountered in nature [18]. It is the simplest PHA with respect to chemical structure, having a methylene (-CH3) group as the pendent R-unit in Fig. 1. Owing to its enzymatic synthesis, PHB has an exceptional stereochemical regularity. The chains are linear and the chiral centers all are in the R-stereochemical conformation, which implies that this polymer is completely isotactic. 

Some of the fragments generated from poly(propylene oxide) pyrolysis contain asymmetric carbon atoms. For example, isomer compounds with two chiral centers are shown below in (R.R) and (R,S) forms ... 

However, there is a wide class of ferroelectric polymers which contains mesogenic units both in the main chain and as lateral substituents [166]. A very high value of spontaneous polarization (500 nC cm ) has recently been reported for a poly(tetramethylene tartrate) with two chiral centers in the backbone and achiral side mesogenic groups [167]... 

Another elegant example of the imitation of the properties of biopolymers by synthetic polymers comes from the school of E. Bayer of Tubingen (172). They have prepared chiral polysiloxane polymers for resolution of optical antipodes. The prochiral polymeric backbone was a copolymer of poly [(2-carboxypropyl)methylsiloxane], octamethylcyclotetrasiloxane, and hexa-methyldisiloxane. Amino acids or small peptides were covalently linked to this polymer in order to introduce a chiral surface. For this, the free carboxyl function of the polymer was reacted with the L-amino acid in the presence of DCC (see Chapter 2). The individual chiral centers (amino acids) on the polymer surface were separated by siloxane chains of specified length in order to achieve optimum interaction with the substrate and polymer viscosity. An example of great value for optical resolution is the polymer designated chirasil-Val, containing 0.86 mmole of iV-tert-butyl-L-valin-amide per gram of polymer (Fig. 5.14). 

Retention of Rohrschneider-McReynolds standards of selected chiral alcohols and ketones was measured to determine the thermodynamic selectivity parameters of stationary phases containing (- -)-61 (M = Pr, Eu, Dy, Er, Yb, n = 3, R = Mef) dissolved in poly(dimethylsiloxane) . Separation of selected racemic alcohols and ketones was achieved and the determined values of thermodynamic enantioselectivity were correlated with the molecular structure of the solutes studied. The decrease of the ionic radius of lanthanides induces greater increase of complexation efficiency for the alcohols than for the ketone coordination complexes. The selectivity of the studied stationary phases follows a common trend which is rationalized in terms of opposing electronic and steric effects of the Lewis acid-base interactions between the selected alcohols, ketones and lanthanide chelates. The retention of over fifty solutes on five stationary phases containing 61 (M = Pr, Eu, Dy, Er, Yb, n = 3, R = Mef) dissolved in polydimethylsiloxane were later measured ". The initial motivation for this work was to explore the utility of a solvation parameter model proposed and developed by Abraham and coworkers for complexing stationary phases containing metal coordination centers. Linear solvation... 

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