Ester-linkages

Macrocyclic peptides and depsipeptides ( macrocyciic peptides with amide and ester linkages) are important natural compounds. They have been synthesized in low yield from open-chain precursors by DCC treatment at high dilution (E. SchrSder, 1963 M.M. Shemyakin,... 

Nucleic acids are acidic substances present m the nuclei of cells and were known long before anyone suspected they were the primary substances involved m the storage transmission and processing of genetic information There are two kinds of nucleic acids ribonucleic acid (RNA) and deoxyribonucleic acid (DNA) Both are complicated biopolymers based on three structural units a carbohydrate a phosphate ester linkage between carbohydrates and a heterocyclic aromatic compound The heterocyclic aro matic compounds are referred to as purine and pyrimidine bases We 11 begin with them and follow the structural thread... 

The other important sequence is the CCA triplet at the 3 end The ammo acid that IS to be transferred is attached through an ester linkage to the terminal 3 oxygen of this sequence All tRNAs have a CCA sequence at their 3 end... 

The mechanistic aspect of these reactions is summarized by saying that the reactions occur in steps. Thus the formation of an ester linkage is not essentially different between two small molecules or in a polyester. 

Fig. 7. Reactions of ttiglycetides at the carbonyl ester linkage. R represents the alkyl side chain.

The ester linkage in the repeating unit characterizes polyesters. R and R represent portions of the monomer molecule that do not participate in the polymerization. They may vary widely, giving rise to many different polyesters. Poly(ethylene terephthalate) (PET), made from ethylene glycol... 

During this early period, a very ingenious free-radical route to polyesters was used to introduce weak linkages into the backbones of hydrocarbon polymers and render them susceptible to bio degradabihty (128—131). Copolymerization of ketene acetals with vinyl monomers incorporates an ester linkage into the polymer backbone by rearrangement of the ketene acetal radical as illustrated in equation 13. The ester is a potential site for biological attack. The chemistry has been demonstrated with ethylene (128—131), acryhc acid (132), and styrene (133). 

The metabohc rate of poly(ester—amide) where x = Q has been studied in rats using carbon-14 labeled polymer. This study indicates that polymer degradation occurs as a result of hydrolysis of the ester linkages whereas the amide linkages remain relatively stable in vivo. Most of the radioactivity is excreted by urine in the form of unchanged amidediol monomer, the polymer hydrolysis product (51). 

Pig. 14. Preparation of biodegradable PS by incorporating ester linkages into the backbone via ring-opening copolymerization of styrene with a cycHc ketene... 

From a bioavailabihty standpoint, the fact that a significant amount of nicotinic acid is in a bound form has important biological consequences. Poor bioavailabihty stems from the fact that the ester linkage is resistance to digestive enzymes. In the case of com, this condition can be alleviated if com is pretreated with alkah. This food preparation method is frequently practiced in Mexico for the preparation of tortillas. 

Both the chemical solubility and the electrical properties are consistent with those expected of a lightly polar polymer, whilst reactivity is consistent with that of a polymer containing hydrolysable carbonate ester linkages partially protected by aromatic hydrocarbon groupings. The influence of these factors on specific properties is amplified in subsequent sections. 

Polyesters are eneountered in many forms. They are important as laminating resins, moulding compositions, fibres, films, surface coating resins, rubbers and plasticisers. The common factor in these widely different materials is that they all contain a number of ester linkages in the main chain. (There are also a number of polymers such as poly(vinyl acetate) which contain a number of ester groups in side chains but these are not generally considered within the term polyester resins.)... 

Esterification. The esterification of rosin provides important commercial products for the adhesive industry. Rosin esters are formed by the reaction of rosins with alcohols at elevated temperatures. Because the carboxyl group of the resin acids is hindered by attachment to a tertiary carbon, esterification with an alcohol can only be accomplished at elevated temperatures. This hindrance is in turn responsible for the high resistance of the resin acid ester linkage to cleavage by water, acid and alkali. 

This reaction is reported to proceed at a rapid rate, with over 25% conversion in less than 0.001 s [3]. It can also proceed at very low temperatures, as in the middle of winter. Most primary substituted urea linkages, referred to as urea bonds, are more thermally stable than urethane bonds, by 20-30°C, but not in all cases. Polyamines based on aromatic amines are normally somewhat slower, especially if there are additional electron withdrawing moieties on the aromatic ring, such as chlorine or ester linkages [4]. Use of aliphatic isocyanates, such as methylene bis-4,4 -(cyclohexylisocyanate) (HnMDI), in place of MDI, has been shown to slow the gelation rate to about 60 s, with an amine chain extender present. Sterically hindered secondary amine-terminated polyols, in conjunction with certain aliphatic isocyanates, are reported to have slower gelation times, in some cases as long as 24 h [4]. 

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